Mono ethylenically unsaturated polymerizable group containing polycarbosiloxane monomers

ABSTRACT

The present invention relates to polymeric compositions useful in the manufacture of biocompatible medical devices. More particularly, the present invention relates to certain monoethylenically unsaturated polymerizable group containing polycarbosiloxane monomers capable of polymerization to form polymeric compositions having desirable physical characteristics useful in the manufacture of ophthalmic devices.

PRIORITY CLAIMS TO PRIOR APPLICATIONS

This patent application is a continuation in part of U.S. patentapplication Ser. No. 12/499,854 filed on Jul. 9, 2009, the contents ofwhich are incorporated by reference herein.

FIELD

The present invention relates to novel monomers useful in themanufacture of biocompatible medical devices. More particularly, thepresent invention relates to certain monomers based on monoethylenically unsaturated polymerizable group containingpolycarbosiloxane monomers capable of polymerization to form polymericcompositions having desirable physical characteristics useful in themanufacture of ophthalmic devices. Such characteristics include lowmodulus of elasticity, improved lubricity and improved hydrolyticstability.

BACKGROUND AND SUMMARY

Various articles, including biomedical devices, are formed oforganosilicon-containing materials. One class oforganosilicon-containing materials useful for biomedical devices, suchas soft contact lenses, is silicone-containing hydrogel materials. Ahydrogel is a hydrated, crosslinked polymeric system that contains waterin an equilibrium state. Hydrogel contact lenses offer relatively highoxygen permeability as well as desirable biocompatibility and comfort.The inclusion of a silicone-containing material in the hydrogelformulation generally provides higher oxygen permeability since siliconebased materials have higher oxygen permeability than water.

Organosilicon-containing materials useful for biomedical devices,including contact lenses, are disclosed in the following U.S. patents:U.S. Pat. No. 4,208,506 (Deichert et al.); U.S. Pat. No. 4,686,267(Ellis et al.); U.S. Pat. No. 5,034,461 (Lai et al.); and U.S. Pat. No.5,070,215 (Bambury et al.).

U.S. Pat. Nos. 5,358,995 and 5,387,632 describe hydrogels made fromvarious combinations of silicone macromers, TRIS, n-vinyl pyrrolidone(NVP) and DMA. Replacing a substantial portion of the silicone macromerwith TRIS reduced the modulus of the resulting hydrogels. Twopublications from the same author, “The Role of Bulky PolysiloxanylalkylMethacrylates in Polyurethane-Polysiloxane Hydrogels”, J. Appl. Poly.Sci., Vol. 60, 1193-1199 (1996), and “The Role of BulkyPolysiloxanylalkyl Methacrylates in Oxygen-Permeable HydrogelMaterials”, J. Appl. Poly. Sci., Vol. 56, 317-324 (1995) also describeexperimental results indicating that the modulus of hydrogels made fromreaction mixtures of silicone-macromers and hydrophilic monomers such asDMA decreases with added TRIS. The addition ofmethacryloxypropyltris(trimethylsiloxy)silane (TRIS) reduced the modulusof such hydrogels, but in many examples the modulus was still higherthan may be desired.

U.S. Pat. No. 4,208,506 describes monomeric polyparaffinsiloxanes cappedwith activated unsaturated groups and polymers and copolymers thereof.The monomers of U.S. Pat. No. 4,208,506 are cross-linkers. However,there still remains a need in the art for new monomers to providesilicone hydrogels which are soft enough to make soft contact lenses,which possess high oxygen permeability, suitable water content, andsufficient elasticity, and are comfortable to the contact lens wearer.

BRIEF DESCRIPTION OF THE DRAWINGS

None.

DETAILED DESCRIPTION

Unless clearly stated otherwise all materials used in forming a monomermix are listed as weight percent. Also, unless clearly stated otherwiseit will be understood that all amounts of materials used to make themonomers and monomer mixes disclosed herein represent the statisticalmean of a normal distribution of weight values such as are ordinarilyencountered in the laboratory or commercial manufacture of the monomersand monomer mixes disclosed herein. Therefore, unless clearly statedotherwise, all numerical values shall be understood as being modified bythe term “about”.

As used herein the expressions “polycarbosiloxane monomer” or “EDS”refer to monomers having at least one -[silyl-alkyl-siloxanyl]-group.The -[silyl-alkyl-siloxanyl]-group may be substituted at any atomcapable of having a substituent group and the -[silyl-alkylsiloxanyl]-group may be a repeating group. The alkyl portion of the[silyl alkyl siloxanyl]-group is a linking group between the silyl andsiloxanyl group and is preferably 2-7 carbon atoms in length.

The term “monomer” used herein refers to varying molecular weightcompounds (i.e. typically having number average molecular weights fromabout 300 to about 100,000) that can be polymerized, and to medium tohigh molecular weight compounds or polymers, sometimes referred to asmacromonomers, (i.e., typically having number average molecular weightsgreater than 600) containing functional groups capable of furtherpolymerization. Thus, it is understood that the terms“organosilicon-containing monomers”, “silicone-containing monomers” and“hydrophilic monomers” include monomers, macromonomers and prepolymers.Prepolymers are partially polymerized monomers or monomers which arecapable of further polymerization.

An “organosilicon-containing monomer” contains at least one [siloxanyl]or at least one [silyl-alkyl-siloxanyl] repeating units, in a monomer,macromer or prepolymer. Preferably, the total Si and attached O arepresent in the organosilicon-containing monomer in an amount greaterthan 5 weight percent, and more preferably greater than 30 weightpercent of the total molecular weight of the organosilicon-containingmonomer. A “silicone-containing monomer” is one that contains at leastone [siloxanyl] repeating units, in a monomer, macromer or prepolymer.

In a first aspect, the invention relates to monomers of formula (I):

wherein X is the residue of a ring opening agent or a capping agent; Lis the same or different and is a linker group or a bond; V is anethylenically unsaturated polymerizable group; R₁, R₂, R₃, R₄, R₅, R₆are independently H, alkyl, halo alkyl, heteroalkyl, cyclo alkyl,heterocyclo alkyl, alkenyl, halo alkenyl, or aromatic; R₇ and R₈ whenpresent are independently H or alkyl wherein at least one of R₇ or R₈ ishydrogen; y is 2-7 and n is 1-100.

Ring opening agents are well known in the literature. Non-limitingexamples of anionic ring opening agents include alkyl lithiums,alkoxides, trialkylsiloxylithium wherein the alkyl group may or may notcontain halo atoms.

Capping agents are well known in the literature. Non-limiting examplesof capping agents include 3-methacryloxypropyldimethylchlorosilane,3-acryloxypropyl dimethylchlorosilane, chlorodimethylsilane andbromodimethylsilane.

Linker groups can be any divalent radical or moiety and includesubstituted or unsubstituted alkyl, alkyl ether, alkenyls, alkenylethers, halo alkyls, substituted or unsubstituted siloxanes, andmonomers capable of propagating ring opening.

Ethylenically unsaturated polymerizable groups are well known to thoseskilled in the art. Non-limiting examples of ethylenically unsaturatedpolymerizable groups would include acrylates, methacrylates, vinylcarbonates, O-vinyl carbamates, N-vinyl carbamates, acrylamides andmethacrylamides.

Additional preferred embodiments of the monomers of the invention hereinwould include monomers of formula (II):

wherein L is the same or different and is a linker group or a bond; V isan ethylenically unsaturated polymerizable group; R₁, R₂, R₃, R₄, R₅, R₆and R₉ are independently H, alkyl, halo alkyl, cyclo alkyl, heterocycloalkyl, alkenyl, halo alkenyl, or aromatic; R₇ and R₈ when present areindependently H or alkyl wherein at least one of R₇ or R₈ is hydrogen; yis 2-7 and n is 1-100.

Additional preferred embodiments of the monomers of the invention hereinwould include monomers of the following formulas III and IV:

wherein R₉, R₁₀ and R₁₁ are independently H, alkyl, haloalkyl or othersubstituted alkyl groups; n is as defined above and n¹ is 0-10; and,

wherein n is 1-100, preferably n is 2-80, more preferably n is 3-20,most preferably n is 5-15.

Additional preferred embodiments of the monomers of the invention hereinwould include monomers of the following formulas V-IX:

Additional preferred embodiments of the monomers of the invention hereinwould include monomers of the following formulas X-XII:

wherein R₉, R₁₀ and R₁₁ are independently H, alkyl, haloalkyl or othersubstituted alkyl groups and n and n¹ are as defined above.

Additional preferred embodiments of the monomers of the invention hereinwould include monomers of the following formulas XIII-XV:

wherein n is as defined above and X⁻ is a counterion to provide anoverall neutral charge.

Counterions capable of providing an overall neutral charge are wellknown to those of ordinary skill in the art and would include, forexample, halide and borate ions.

An additional preferred embodiment of the monomers of the inventionherein would include the monomer of the following formula XVI:

Monomers of formula I can be prepared by various synthetic methods, forexample:

Monomers of formula II can be prepared by various synthetic methods, forexample as shown in Example 6.

In yet another aspect, the invention includes articles formed of deviceforming monomer mixes comprising, alone or in combination, any of themonomers of formulas I-XVI. According to preferred embodiments, thearticle is the polymerization product of a mixture comprising at leastone of the aforementioned monomers of formulas I-XVI and at least asecond copolymerizable monomer. The invention is applicable to a widevariety of polymeric materials, either rigid or soft ophthalmicmaterials for implantation on or in an eye. Especially preferredpolymeric materials are ophthalmic lenses including contact lenses,phakic and aphakic intraocular lenses and corneal implants although allpolymeric materials including biomaterials are contemplated as beingwithin the scope of this invention. Preferred articles are opticallyclear and useful as a contact lens.

The monomer mix of the present invention also provides medical devicessuch as artificial heart valves, buttons for lathing lenses, films,surgical devices, vessel substitutes, intrauterine devices, membranes,diaphragms, surgical implants, artificial blood vessels, artificialureters, artificial breast tissue and membranes intended to come intocontact with body fluid outside of the body, e.g., membranes for kidneydialysis and heart/lung machines and the like, catheters, mouth guards,denture liners, ophthalmic devices, and especially hydrogel contactlenses.

As set forth above, unless clearly stated otherwise it will beunderstood that all amounts of materials used to make the monomers andmonomer mixes disclosed herein represent the statistical mean of anormal distribution of weight values such as are ordinarily encounteredin the laboratory or commercial manufacture of the monomers and monomermixes disclosed herein. Therefore, unless clearly stated otherwise, allnumerical values shall be understood as being modified by the term“about”.

Useful concentration of the mono ethylenically unsaturated polymerizablegroup containing polycarbosiloxane monomers of the invention hereinwould be 0.1 to 30 percent by weight of the monomer mix. More preferredconcentrations are 0.1 to 20 percent by weight. Even more preferredconcentrations would be 5 to 15 percent by weight.

Preferred compositions of the monomer mix have both hydrophilic andhydrophobic monomers. Depending upon the specific application, usefularticles made with these materials may require additional (other thanthe subject mono ethylenically unsaturated polymerizable groupcontaining polycarbosiloxane monomers) hydrophobic, possibly siliconecontaining monomers. These additional silicone containing hydrophobicmonomers will be present at between 0.1 to 75.8 percent by weight, morepreferably between 2 to 20 percent by weight, even more preferablybetween 5 to 13 percent by weight. Amounts of non-silicone containinghydrophobic monomers will be 0 to 60 percent by weight. Examples ofnon-silicone hydrophobic materials include alkyl acrylates andmethacrylates. Especially preferred is silicone-containing hydrogelforming materials.

Depending upon the application, useful articles may also require bulkymonomers such as those disclosed in U.S. Pat. No. 6,921,802 whichinclude methacryloxypropyl tris(trimethylsiloxy)silane (“TRIS”),pentamethyldisiloxanyl methylmethacrylate,tris(trimethylsiloxy)methacryloxy propylsilane,phenyltretramethyl-disloxanylethyl acrylate,methyldi(trimethylsiloxy)methacryloxymethyl silane,3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate,3[tris(trimethylsiloxy)silyl]propyol allyl carbamate, and3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate. These bulkymonomers, when present, may be present at 0 to 41.2 percent by weight,34 to 41 percent by weight or even 25 to 41 percent by weight.

Organosilicon-containing hydrogels are prepared by polymerizing amixture containing at least one organosilicon-containing monomer and atleast one hydrophilic monomer. Additionally, a silicone-containingmonomer which functions as a crosslinking agent (a crosslinker beingdefined as a monomer having multiple polymerizable functionalities) or aseparate crosslinker may be employed. Hydrophobic crosslinkers wouldinclude methacrylates such as ethylene glycol dimethacrylate (EGDMA) andallyl methacrylate (AMA). Methacrylamide crosslinkers such as Ma2D37allow the incorporation of greater amounts hydrophilic comonomers intothe monomer mix than its methacrylate counterparts. This greater amountof hydrophilic comonomers provides a finished lens with higher watercontent and improved wetability. Amounts of cross-linker would bebetween 0 to 76 percent by weight, 2 to 20 percent by weight or 5 to 13percent by weight.

The mono ethylenically unsaturated polymerizable group containingpolycarbosiloxane monomers of the invention herein may be copolymerizedwith a wide variety of hydrophilic monomers to produce silicone hydrogellenses. Suitable hydrophilic monomers include: unsaturated carboxylicacids, such as methacrylic and acrylic acids; acrylic substitutedalcohols, such as 2-hydroxyethyl methacrylate and 2-hydroxyethylacrylate; vinyl lactams, such as N-vinylpyrrolidone (NVP) and1-vinylazonan-2-one; and acrylamides, such as methacrylamide andN,N-dimethylacrylamide (DMA). These hydrophilic monomers will bepresent, separately or by combined weight in amounts of between 0 to 60percent by weight, between 20 to 45 percent by weight, between 0 to 48.6percent by weight, between 0 to 30 percent by weight, between 0 to 25percent by weight, between 0 to 9.5 percent by weight or between 2 to 7percent by weight.

Other examples of silicone-containing monomer mixtures which may be usedwith this invention include the following: vinyl carbonate and vinylcarbamate monomer mixtures as disclosed in U.S. Pat. Nos. 5,070,215 and5,610,252 (Bambury et al); fluorosilicon monomer mixtures as disclosedin U.S. Pat. Nos. 5,321,108; 5,387,662 and 5,539,016 (Kunzler et al.);fumarate monomer mixtures as disclosed in U.S. Pat. Nos. 5,374,662;5,420,324 and 5,496,871 (Lai et al.) and urethane monomer mixtures asdisclosed in U.S. Pat. Nos. 5,451,651; 5,648,515; 5,639,908 and5,594,085 (Lai et al.), all of which are commonly assigned to assigneeherein Bausch & Lomb Incorporated, and the entire disclosures of whichare incorporated herein by reference. Other suitable hydrophilicmonomers will be apparent to one skilled in the art.

An organic diluent may be included in the initial monomeric mixture. Asused herein, the term “organic diluent” encompasses organic compoundswhich minimize incompatibility of the components in the initialmonomeric mixture and are substantially nonreactive with the componentsin the initial mixture. Additionally, the organic diluent serves tominimize phase separation of polymerized products produced bypolymerization of the monomeric mixture. Also, the organic diluent willgenerally be relatively non-inflammable.

Contemplated organic diluents include alcohols such as tert-butanol(TBA), tert-amyl alcohol, hexanol and nonanol; diols, such as ethyleneglycol; and polyols, such as glycerol. Preferably, the organic diluentis sufficiently soluble in the extraction solvent to facilitate itsremoval from a cured article during the extraction step. Other suitableorganic diluents would be apparent to a person of ordinary skill in theart.

The organic diluent is included in an amount effective to provide thedesired effect (for example, minimal phase separation of polymerizedproducts). Generally, the diluent is included at 0 to 60% by weight ofthe monomeric mixture, with 1 to 40% by weight being more preferred, 2to 30% by weight being even more preferred and 3 to 25% by weight beingespecially preferred.

According to the present process, the monomeric mixture, comprising atleast one hydrophilic monomer, at least one mono ethylenicallyunsaturated polymerizable group containing polycarbosiloxane monomer andoptionally the organic diluent, is shaped and cured by conventionalmethods such as static casting or spincasting.

Lens formation can be by free radical polymerization using initiatorssuch as azobisisobutyronitrile (AIBN) and peroxide catalysts underconditions such as those set forth in U.S. Pat. No. 3,808,179,incorporated herein by reference. Photoinitiation of polymerization ofthe monomer mixture using initiators such as IRGACURE 819(Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide) and DAROCURE 1173(2-Hydroxy-2-methyl-1-phenyl-propan-1-one) are also well known in theart and may be used in the process of forming an article as disclosedherein. By careful selection of the appropriate wavelength of light toconduct photo polymerization of the monomer mix a finished producthaving desirable properties such as surface hydrophilicity and surfacelubricity can result. Other reaction conditions important to photopolymerization would include incident light intensity, light exposuretime and controlled atmosphere can also be critical to providing asuccessful commercial product. Suitable light intensity will depend uponpolymerization conditions such as the mold material, monomer mix andinitiator concentration ratio. For example, suitable intensities wouldrange from 1.0 mW/cm2 to 25.0 mW/cm2. Similarly, light exposure time canvary, depending upon polymerization conditions. Therefore, lightexposure time may range from one minute to 60 minutes. Control ofatmospheric conditions for polymerizing contact lenses is well known inthe art. Colorants and the like may be added prior to monomerpolymerization.

Subsequently, a sufficient amount of unreacted monomer and, whenpresent, organic diluent is removed from the cured article to improvethe biocompatibility of the article. Release of non-polymerized monomersinto the eye upon installation of a lens can cause irritation and otherproblems. Therefore, once the biomaterials formed from the polymerizedmonomer mix containing the monomers disclosed herein are formed they arethen extracted to prepare them for packaging and eventual use.Extraction is accomplished by exposing the polymerized materials tovarious solvents such as water, 2-propanol, etc. for varying periods oftime. For example, one extraction process is to immerse the polymerizedmaterials in water for about three minutes, remove the water and thenimmerse the polymerized materials in another aliquot of water for aboutthree minutes, remove that aliquot of water and then autoclave thepolymerized material in water, buffer solution or other packagingsolution.

Surface structure and composition determine many of the physicalproperties and ultimate uses of solid materials. Characteristics such aswetting, friction, and adhesion or lubricity are largely influenced bysurface characteristics. The alteration of surface characteristics is ofspecial significance in biotechnical applications where biocompatibilityis of particular concern. It should be remembered that in coatingmedical devices the term “surface” is not to be limited to meaning “atleast one complete surface”. Surface coverage does not have to be evenor complete to be effective for surface functionality or surfacetreatment. Thus, it is desired to provide an organosilicon containinghydrogel contact lens with an optically clear, hydrophilic surface filmthat will not only exhibit improved wetability, but which will generallyallow the use of an organosilicon containing hydrogel contact lens inthe human eye for extended period of time. In the case of aorganosilicon containing hydrogel lens for extended wear, it may befurther desirable to provide an improved organosilicon-containinghydrogel contact lens with an optically clear surface film that will notonly exhibit improved lipid and microbial behavior, but which willgenerally allow the use of a organosilicon-containing hydrogel contactlens in the human eye for an extended period of time. Such a surfacetreated lens would be comfortable to wear in actual use and allow forthe extended wear of the lens without irritation or other adverseeffects to the cornea.

It may also be desirable to apply these surface enhancing coatings toimplantable medical devices such as intraocular lens materials to reducethe attachment of lens epithelial cells to the implanted device and toreduce friction as the intraocular lens passes through an inserter intothe eye. Therefore, if needed to produce a successful commercial productthe polymerized materials may optionally be coated.

Methods of coating contact lenses and various types of coatings forcontact lenses are well known to those of ordinary skill in the art.Methods of coating the substrate include dip coating of the substrateinto a solution containing the surface coating material. The solutioncontaining the surface coating material may contain substantially thesurface coating material in solvent or may contain other materials suchas cleaning and extracting materials. Other methods could include spraycoating the device with the surface coating material. In certainembodiments, it may be necessary to use suitable catalysts, for example,a condensation catalyst. Alternatively, the substrate and the othersurface coating material may be subjected to autoclave conditions. Incertain embodiments, the substrate and the surface coating material maybe autoclaved in the packaging material that will contain the coatedsubstrate. Once the interaction between the substrate and the surfacecoating material has occurred, the remaining surface modifying agentcould be substantially removed and packaging solution added to thesubstrate packaging material. Sealing and other processing steps thenproceed as they usually do. Alternatively, the surface modifying agentcould be retained in the substrate packaging material during storage andshipping of the substrate device to the end user.

Coatings for medical devices are typically oligomeric or polymeric andsized to provide suitable properties to the surface of the medicaldevice to be coated. Coatings according to certain embodiments of theinvention herein will typically contain hydrophilic domain(s) showinggood surface properties when the coating is associated with thesubstrate (i.e., the uncoated medical device). The hydrophilic domain(s)will comprise at least one hydrophilic monomer, such as, HEMA, glycerylmethacrylate, methacrylic acid (“MAA”), acrylic acid (“AA”),methacrylamide, acrylamide, N,N′-dimethylmethacrylamide, orN,N′-dimethylacrylamide; copolymers thereof; hydrophilic prepolymers,such as ethylenically unsaturated poly(alkylene oxide)s, cyclic lactamssuch as N-vinyl-2-pyrrolidone (“NVP”), or derivatives thereof. Stillfurther examples are the hydrophilic vinyl carbonate or vinyl carbamatemonomers. Hydrophilic monomers can be nonionic monomers, such as2-hydroxyethyl methacrylate (“HEMA”), 2-hydroxyethyl acrylate (“HEA”),2-(2-ethoxyethoxy)ethyl(meth)acrylate, glyceryl (meth)acrylate,poly(ethylene glycol (meth)acrylate), tetrahydrofurfuryl(meth)acrylate,(meth)acrylamide, N,N′-dimethylmethacrylamide,N,N′-dimethylacrylamide(“DMA”), N-vinyl-2-pyrrolidone (or other N-vinyllactams), N-vinyl acetamide, and combinations thereof. Still furtherexamples of hydrophilic monomers are the vinyl carbonate and vinylcarbamate monomers disclosed in U.S. Pat. No. 5,070,215, and thehydrophilic oxazolone monomers disclosed in U.S. Pat. No. 4,910,277. Thecontents of these patents are incorporated herein by reference. Thehydrophilic monomer also can be an anionic monomer, such as2-methacryloyloxyethylsulfonate salts. Substituted anionic hydrophilicmonomers, such as from acrylic and methacrylic acid, can also beutilized wherein the substituted group can be removed by a facilechemical process. Non-limiting examples of such substituted anionichydrophilic monomers include trimethylsilyl esters of (meth)acrylicacid, which are hydrolyzed to regenerate an anionic carboxyl group. Thehydrophilic monomer also can be a cationic monomer selected from thegroup consisting of 3-methacrylamidopropyl-N,N,N-trimethyammonium salts,2-methacryloyloxyethyl-N,N,N-trimethylammonium salts, andamine-containing monomers, such as 3-methacrylamidopropyl-N,N-dimethylamine. Other suitable hydrophilic monomers will be apparent to oneskilled in the art.

Generally, a packaging system for the storage of an ophthalmic lensaccording to the present invention includes at least a sealed containercontaining one or more unused ophthalmic lenses immersed in an aqueouslens packaging solution. Preferably, the sealed container is ahermetically sealed blister-pack, in which a concave well containing acontact lens is covered by a metal or plastic sheet adapted for peelingin order to open the blister-pack. The sealed container may be anysuitable generally inert packaging material providing a reasonabledegree of protection to the lens, preferably a plastic material such aspolyalkylene, PVC, polyamide, and the like.

Organosilicon containing substrates are generally hydrophobic. Toimprove the patient experience, especially as regards to comfort, it isnot unusual to utilize a packaging solution or other method to reducethe hydrophobic character of the substrate or to provide a ready to useproduct with improved lubricity. The relative hydrophobic character of asurface can be measured by many means known to those of ordinary skillin the art. One example of a method of contact angle measurement isSessile Drop technique. For organosilicon containing substrates a highsessile drop contact angle is some indication of a relativelyhydrophobic material (in the dry state). Based upon empiricalobservations, packaging solutions that provide a material having asessile drop contact angle less than about 75 degrees are relativelyhydrophilic and tend to easily slide about a hydrophobic surface such asthat provided by a polystyrene Petri dish when a force such as appliedby a hand held scalpel is used to slice the material (in this case amolded contact lens). Other packaging materials that provide a materialhaving a sessile drop contact angle greater than about 75 degrees arerelatively hydrophobic and tend to adhere to a hydrophobic surface suchas that provided by a polystyrene Petri dish. It has surprisingly beendiscovered that when a organosilicon hydrogel material is packaged witha borate buffered polyphosphocholine solution the lens behaves as if itwere packaged with a more hydrophobic material providing packagingsolution (e.g., sessile drop contact angle greater than about 75degrees) yet behaves as lubricious as a material packaged with apackaging solution that provides a material having a sessile dropcontact angle less than about 75 degrees. Therefore a medical devicepackaged with a borate buffered polyphosphocholine solution is apreferred embodiment of the invention herein.

Suitable packaging solution material selection will depend upon aparticular lens formulation and is therefore somewhat broad in nature.Below are nonlimiting examples of representative cationic, anionic, andzwitterionic polymers or components, along with non-ionic surfactantsand peptide-based materials which are useful in packaging solutions(depending upon the intended use).

Anionic Polymers

Poly(acrylic acid)

Poly(acrylamide-co-acrylic acid)

Carboxymethylcellulose

Cationic Polymers

Polymer JR

Polymers having latent amines

Zwitterionic Components Phosphocholine

Latent amino acids

Polypeptides

Poly(glutamic acid)

Poly(lysine)

Non-Ionic Surfactants

Tetronic T1107

Tetronic T908

Hydroxypropyl methylcellulose

Silicone surfactants (NVP-co-TRIS VC)

Glycereth cocoate

For the sake of simplicity the following discussion of packagingsolutions will focus upon nonionic polymeric conditioning agents. Itwill be recognized that in general the selection of an appropriatepackaging solution for the ophthalmic device formed from a polymerizedmonomer mix containing monomers based on mono ethylenically unsaturatedpolymerizable group containing polycarbosiloxane monomers is within thepurview of one of ordinary skill in the art. However, as noted above,certain packaging solutions used with an organosilicon containing devicemay be inventive in their own right.

Any suitable nonionic polymeric conditioning agent component may beemployed in accordance with the present invention provided that itfunctions as described herein and has no substantial detrimental effecton the contact lens being stored or on the wearer of the contact lens.This component is ophthalmically acceptable at the concentrations used.Particularly useful components are those, which are water soluble, forexample, soluble at the concentrations used in the presently usefulliquid aqueous media.

These compounds condition the lens by providing one or more of thefollowing attributes: increased viscosity for increased retention timeon the lens; enhanced wetting of the lens surface; decreased surfacefriction (i.e., improved lubricity); or enhanced comfort of a contactlens by forming a cushioning film over the lens surface.

A class of nonionic, polymeric conditioning agents includes nonionicpolysaccharides. Representative examples of suitable components for useherein include, but are not limited to, methylcellulose;hydroxyethylcellulose; hydroxypropylcellulose;hydroxypropylmethylcellulose; and methylhydroxyethyl starches.

Another class of nonionic, polymeric conditioning agents includespolyvinylalcohols and polyvinylpyrrolidones.

Another class of nonionic, polymeric conditioning agents includespolymers of PEO, including PEO homopolymers, and block copolymers of PEOand PPO. This class includes poloxamers and poloxamines, including thosedisclosed in U.S. Pat. No. 6,440,366.

The above classes of nonionic, polymeric conditioning agents areintended for illustrative purposes only and not to limit the scope ofthe present invention. Such polymers are known to those of skill in theart.

Generally, the average molecular weight of nonionic, polymericconditioning agent is a minimum of about 1 kDa and a maximum of about700 kDa, more preferably, about 5 kDa to 500 kDa.

The amount of nonionic, polymeric conditioning agent employed is thatamount effective to improve the surface properties of the ophthalmicdevice when combined with a nonionic, nonpolymeric polyol. Preferablythe nonionic, polymeric conditioning agent is present in the packagingsolution of the invention in an amount of at least 0.01% w/v. Thespecific amount of such component used can vary widely depending on anumber of factors, for example, the specific polymeric component andnonionic polyol being employed. Generally, the concentration of thenonionic, polymeric conditioning agent is from about 0.01 to about 10%w/w and preferably from about 0.5 to about 1.5% w/w.

In one embodiment, the nonionic, nonpolymeric polyol for use herein canbe a nonionic polyol containing 2 to about 12 carbon atoms andpreferably 2 to 4 carbon atoms and from 2 to 8 hydroxyl groups.Representative examples of such nonionic polyols include glycerin,ethylene glycol, propylene glycol, sorbitol, mannitol, monosaccarides,disaccharides such as trehalose, and the like and mixtures thereof. Inone embodiment, the nonionic polyol can be glycerin, ethylene glycol,sorbitol, mannitol, monosaccharides and mixtures thereof.

The amount of the nonionic, nonpolymeric polyol in the packagingsolution will generally be an amount sufficient to form a more uniformcoating on the surface of the lens when packaged in a packaging solutionaccording to the present invention. In general, the concentration of thenonionic polyol will ordinarily range from about 0.01 to about 10% w/wand preferably from about 0.1 to about 3.0% w/w.

The packaging solutions according to the present invention arephysiologically compatible. Specifically, the solution must be“ophthalmically safe” for use with a lens such as a contact lens,meaning that a contact lens treated with the solution is generallysuitable and safe for direct placement on the eye without rinsing, thatis, the solution is safe and comfortable for daily contact with the eyevia a contact lens that has been wetted with the solution. Anophthalmically safe solution has a tonicity and pH that is compatiblewith the eye and includes materials, and amounts thereof, that arenon-cytotoxic according to ISO standards and U.S. Food & DrugAdministration (FDA) regulations. The solution should be sterile in thatthe absence of microbial contaminants in the product prior to releasemust be statistically demonstrated to the degree necessary for suchproducts. The liquid media useful in the present invention are selectedto have no substantial detrimental effect on the lens being treated orcared for and to allow or even facilitate the present lens treatment ortreatments. The liquid media are preferably aqueous-based. Aparticularly useful aqueous liquid medium is that derived from saline,for example, a conventional saline solution or a conventional bufferedsaline solution.

The pH of the present solutions should be maintained within the range ofabout 6.0 to about 8, and preferably about 6.5 to about 7.8. Suitablebuffers may be added, such as: phosphate; borate; citrate; carbonate;tris-(hydroxymethyl)aminomethane (TRIS);bis(2-hydroxyethyl)-imino-tris-(hydroxymethyl)aminoalcohol (bis-tris);zwitterionic buffers such asN-[2-Hydroxy-1,1-bis(hydroxymethyl)ethyl]glycine (Tricine) andN-[2-Hydroxy-1,1-bis(hydroxymethyl)ethyl]glycine, MOPS;N-(Carbamoylmethyl)taurine (ACES); amino acids and amino acidderivatives; and mixtures thereof. Generally, buffers will be used inamounts ranging from about 0.05 to about 2.5 percent by weight, andpreferably from about 0.1 to about 1.5 percent by weight of thesolution. The packaging solutions of this invention preferably contain aborate buffer, containing one or more of boric acid, sodium borate,potassium tetraborate, potassium metaborate or mixtures of the same.

If needed, the solutions of the present invention may be adjusted withtonicity agents, to approximate the osmotic pressure of normal lacrimalfluids, which is equivalent to a 0.9 percent solution of sodium chlorideor 2.5 percent of glycerol solution. The solutions are madesubstantially isotonic with physiological saline used alone or incombination, otherwise if simply blended with sterile water and madehypotonic or made hypertonic the lenses will lose their desirableoptical parameters. Correspondingly, excess saline may result in theformation of a hypertonic solution, which will cause stinging, and eyeirritation.

Examples of suitable tonicity adjusting agents include, but are notlimited to, sodium and potassium chloride, dextrose, calcium andmagnesium chloride and the like and mixtures thereof. These agents aretypically used individually in amounts ranging from about 0.01 to about2.5% w/v and preferably from about 0.2 to about 1.5% w/v. Preferably,the tonicity agent will be employed in an amount to provide a finalosmotic value of at least about 200 mOsm/kg, preferably from about 200to about 450 mOsm/kg, more preferably from about 250 to about 400mOsm/kg, and most preferably from about 280 to about 370 mOsm/kg.

If desired, one or more additional components can be included in thepackaging solution. Such additional component or components are chosento impart or provide at least one beneficial or desired property to thepackaging solution. Such additional components may be selected fromcomponents that are conventionally used in one or more ophthalmic devicecare compositions. Examples of such additional components includecleaning agents, wetting agents, nutrient agents, sequestering agents,viscosity builders, contact lens conditioning agents, antioxidants, andthe like and mixtures thereof. These additional components may each beincluded in the packaging solutions in an amount effective to impart orprovide the beneficial or desired property to the packaging solutions.For example, such additional components may be included in the packagingsolutions in amounts similar to the amounts of such components used inother, e.g., conventional, contact lens care products.

Useful sequestering agents include, but are not limited to, disodiumethylene diamine tetra acetate, alkali metal hexametaphosphate, citricacid, sodium citrate and the like and mixtures thereof.

Useful antioxidants include, but are not limited to, sodiummetabisulfite, sodium thiosulfate, N-acetylcysteine, butylatedhydroxyanisole, butylated hydroxytoluene and the like and mixturesthereof.

The method of packaging and storing an ophthalmic lens according to thepresent invention includes at least packaging the ophthalmic lensimmersed in the aqueous contact lens packaging solution described above.The method may include immersing the ophthalmic lens in an aqueouscontact lens solution prior to delivery to the customer/wearer directlyfollowing manufacture of the contact lens. Alternately, the packagingand storing in the solution of the present invention may occur at anintermediate point before delivery to the ultimate customer (wearer) butfollowing manufacture and transportation of the lens in a dry state,wherein the dry lens is hydrated by immersing the lens in the contactlens packaging solution. Consequently, a package for delivery to acustomer may include a sealed container containing one or more unusedcontact lenses immersed in an aqueous contact lens packaging solutionaccording to the present invention.

In one embodiment, the steps leading to the present ophthalmic devicepackaging system include (1) molding an ophthalmic device in a moldcomprising at least a first and second mold portion, (2) removing thelens from the mold portions; (3) introducing the packing solution ofthis invention and the ophthalmic lens into the container, and (4)sealing the container. Preferably, the method also includes the step ofsterilizing the contents of the container. Sterilization may take placeprior to, or most conveniently after, sealing of the container and maybe effected by any suitable method known in the art, e.g., by balancedautoclaving of the sealed container at temperatures of about 120° C. orhigher. Preferred packages are plastic blister packages, including arecess for receiving a contact lens and the package solution, where therecess is sealed with lidstock prior to sterilization of the packagecontents. Especially preferred packages would include a disposablepackage and package assembly for contact lenses. A single packagecomprises a flange with a well formed therein for holding a contact lensin solution. A flexible cover sheet extends over the flange and issealed about the perimeter of the well to seal the lens and solution inthe well. The cover sheet may be easily peeled from the flange by a userto access the lens held therein. First and second support structures areformed opposite each other and extend generally perpendicularly from theflange. The support structures are configured to stably support thepackage on a flat surface such as a table.

Each support structure includes a major wall and a minor wall lying ingenerally spaced, parallel planes to each other although the major andminor walls may interconnect or touch along one or more points thereof.In a preferred embodiment, the minor wall is located inwardly of arespective major wall.

A package assembly is also disclosed including a second packageconfigured substantially the same as a first package wherein the firstand second packages may be releasably attached to each other with thefirst and second support structures of each in meshing engagement witheach other.

In certain embodiments, following extraction of unreacted monomers andany organic diluent, the shaped article, for example an RGP lens, isoptionally machined by various processes known in the art. The machiningstep includes lathe cutting a lens surface, lathe cutting a lens edge,buffing a lens edge or polishing a lens edge or surface. The presentprocess is particularly advantageous for processes wherein a lenssurface is lathe cut, since machining of a lens surface is especiallydifficult when the surface is tacky or rubbery.

Generally, such machining processes are performed before the article isreleased from a mold part. After the machining operation, the lens canbe released from the mold part and hydrated. Alternately, the articlecan be machined after removal from the mold part and then hydrated.

The following examples are provided to enable one skilled in the art topractice the invention and are merely illustrative of the invention. Theexamples should not be read as limiting the scope of the invention asdefined in the claims.

EXAMPLES

All solvents and reagents were obtained from commercially availablesources and used as received.

Analytical Measurements

ESI-TOF MS: The electrospray (ESI) time of flight (TOF) MS analysis wasperformed on an Applied Biosystems Mariner instrument. The instrumentoperated in positive ion mode. The instrument was mass calibrated with astandard solution containing lysine, angiotensinogen, bradykinin(fragment 1-5) and des-Pro bradykinin. This mixture provides aseven-point calibration from 147 to 921 m/z. The applied voltageparameters were optimized from signal obtained from the same standardsolution. For exact mass measurements poly(ethylene glycol) (PEG),having a nominal M_(n) value of 400 Da, was added to the sample ofinterest and used as an internal mass standard. Two PEG oligomers thatbracketed the sample mass of interest were used to calibrate the massscale. Samples were prepared as 30 μM solutions in isopropanol (IPA)with the addition of 2% by volume saturated NaCl in IPA. Samples weredirectly infused into the ESI-TOF MS instrument at a rate of 35 μL/min.A sufficient resolving power (6000 RP m/Δm FWHM) was achieved in theanalysis to obtain the monoisotopic mass for each sample. In eachanalysis the experimental monoisotopic mass was compared to thetheoretical monoisotopic mass as determined from the respectiveelemental compositions. In each analysis the monoisotopic masscomparison was less than 10 ppm error. It should be noted that unchargedsamples have a sodium (Na) atom included in their elemental composition.This Na atom occurs as a necessary charge agent added in the samplepreparation procedure. Some samples do not require an added charge agentsince they contain a charge from the quaternary nitrogen inherent totheir respective structure.

GC: Gas chromatography was performed using a Hewlett Packard HP 6890Series GC System. Purities were determined by integration of the primarypeak and comparison to the normalized chromatograph.

NMR: ¹H-NMR characterization was carried out using a 400 MHz Varianspectrometer using standard techniques in the art. Samples weredissolved in chloroform-d (99.8 atom % D), unless otherwise noted.Chemical shifts were determined by assigning the residual chloroformpeak at 7.25 ppm. Peak areas and proton ratios were determined byintegration of baseline separated peaks. Splitting patterns (s=singlet,d=doublet, t=triplet, q=quartet, m=multiplet, br=broad) and couplingconstants (J/Hz) are reported when present and clearly distinguishable.

Mechanical properties and Oxygen Permeability: Modulus and elongationtests were conducted according to ASTM D-1708a, employing an Instron(Model 4502) instrument where the hydrogel film sample is immersed inborate buffered saline; an appropriate size of the film sample is gaugelength 22 mm and width 4.75 mm, where the sample further has endsforming a dog bone shape to accommodate gripping of the sample withclamps of the Instron instrument, and a thickness of 200+50 microns.

Oxygen permeability (also referred to as Dk) was determined by thefollowing procedure. Other methods and/or instruments may be used aslong as the oxygen permeability values obtained therefrom are equivalentto the described method. The oxygen permeability of silicone hydrogelsis measured by the polarographic method (ANSI Z80.20-1998) using an O2Permeometer Model 201T instrument (Createch, Albany, Calif. USA) havinga probe containing a central, circular gold cathode at its end and asilver anode insulated from the cathode. Measurements are taken only onpre-inspected pinhole-free, flat silicone hydrogel film samples of threedifferent center thicknesses ranging from 150 to 600 microns. Centerthickness measurements of the film samples may be measured using aRehder ET-1 electronic thickness gauge. Generally, the film samples havethe shape of a circular disk. Measurements are taken with the filmsample and probe immersed in a bath containing circulating phosphatebuffered saline (PBS) equilibrated at 35° C.+/−0.2°. Prior to immersingthe probe and film sample in the PBS bath, the film sample is placed andcentered on the cathode premoistened with the equilibrated PBS, ensuringno air bubbles or excess PBS exists between the cathode and the filmsample, and the film sample is then secured to the probe with a mountingcap, with the cathode portion of the probe contacting only the filmsample. For silicone hydrogel films, it is frequently useful to employ aTeflon polymer membrane, e.g., having a circular disk shape, between theprobe cathode and the film sample. In such cases, the Teflon membrane isfirst placed on the pre-moistened cathode, and then the film sample isplaced on the Teflon membrane, ensuring no air bubbles or excess PBSexists beneath the Teflon membrane or film sample. Once measurements arecollected, only data with correlation coefficient value (R2) of 0.97 orhigher should be entered into the calculation of Dk value. At least twoDk measurements per thickness, and meeting R2 value, are obtained. Usingknown regression analyses, oxygen permeability (Dk) is calculated fromthe film samples having at least three different thicknesses. Any filmsamples hydrated with solutions other than PBS are first soaked inpurified water and allowed to equilibrate for at least 24 hours, andthen soaked in PHB and allowed to equilibrate for at least 12 hours. Theinstruments are regularly cleaned and regularly calibrated using RGPstandards. Upper and lower limits are established by calculating a+/−8.8% of the Repository values established by William J. Benjamin, etal., The Oxygen Permeability of Reference Materials, Optom Vis Sci 7(12s): 95 (1997), the disclosure of which is incorporated herein in itsentirety:

MATERIAL UPPER NAME REPOSITORY VALUES LOWER LIMIT LIMIT Fluoroperm 3026.2 24 29 Menicon EX 62.4 56 66 Quantum II 92.9 85 101

ABBREVIATIONS

NVP 1-Vinyl-2-pyrrolidone

TRIS 3-Methacryloxypropyltris(trimethylsiloxy)silane

HEMA 2-Hydroxyethyl methacrylatev-64 2,2′-Azobis(2-methylpropionitrile)EGDMA ethylene glycol dimethacrylateBHT butylated hydroxytoluene

Unless otherwise specifically stated or made clear by its usage, allnumbers used in the examples should be considered to be modified by theterm “about” and to be weight percent.

Example 1 Synthesis of M1-EDS7-TMS

2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (19.2 g, 0.12 mol) wastaken in 50 mL of dry cyclohexane under N₂ and stirred for 30 minutes at25° C. To this mixture lithium trimethylsilanolate (1.92 g, 0.02 mol)was added with stirring. After 1 hour dry THF (25 mL) was added and thereaction mixture continued to stir for 24 hours at 25° C.Dimethylchlorosilane (1.9 g, 0.02 mol) was then added and a color changewas observed. Stirring was continued for 3 hours more and the reactionmixture was then filtered. The filtrate was concentrated under vacuum togive clear oil in 22 g yield as the expected product based on the methodof preparation and characterized by NMR, SEC and MALDI showing about 7condensed 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane ring openunits. The filtrate was used as is for hydrosilation by taking intotoluene (20 mL) and adding allylmethacrylate (3.15 g, 0.025 mol, ˜25mmol) under N₂ atmosphere followed by the addition ofplatinum(0)1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex 3 wt %solution in xylene (as catalyst). The reaction mixture was stirred for 6hours at 40-45° C. Stripping of the solvent on rotovap and then underhigh vacuum to give a yellow oil in 17 g yield as the desired productM1-EDS7-TMS characterized by MALDI.

Example 2 Synthesis of M1-EDS6-TMS

To an oven dried 2 L two-neck round bottom flask equipped with amagnetic stirring bar and condenser under N2 atmosphere were added2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (77.22 g, 0.482 mol)and anhydrous cyclohexane (150 mL) under stirring in N₂ atmosphere.Lithium trimethyl silanolate (7.2 g, 0.0749 mol) was added to the abovereaction mixture followed by the addition of cyclohexane (25 mL). Afterstirring for one hour, THF (70 mL, distilled over Na/Benzophenone) wasadded and the reaction mixture continued to stir for 16 hours.Methylacryloxypropyl dimethylchlorosilane (20 g, 0.09 mol) was thenadded and the mixture stirred for another 24 hours. Reaction mixture wasthen filtered and Silica gel (3.5 g, dried at 160° C. for 3 hours) wasthen added and the reaction mixture stirred another 4 hours. Reactionmixture was then filtered thru a bed of Celite (20 g) and BHT (5 mg) wasadded to the filtrate. The filtrate was then concentrated under vacuum(40° C./0.3 mm Hg). Heptane (200 mL) was then added to the concentratewith shaking and washed with DI water (100 mL), aqueous NaHCO₃ (2×100mL, prepared by dissolving 10 g NaHCO₃ in 200 mL DI water), brine (100mL) and finally DI water (100 mL). Heptane (50 mL) was then added anddried over MgSO₄ (15 g) for 20 hours. MgSO₄ was filtered off and thesolvent was removed on rotary evaporator. The crude product was stirredover activated basic Alumina (30 g for 24 h) and then filtered over athin bed of Celite. Striping off any residue solvent at 25° C. at 0.2mmHg for 30 minutes yielded the desired product M1-EDS6-TMS as a clearoil in 80 g quantity. It was characterized by NMR, GPC, GC-MS and MALDI.

Example 3 Synthesis of M1-EDS9-TMS

2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (14.4 g, 0.09 mol) wastaken in 35 mL of dry cyclohexane under N₂ and stirred for 10 minutes at25° C. To this lithium trimethylsilanolate (960 mg, 0.01 mol) was addedwith stirring. After 2 hours dry THF (20 mL) was added and the reactionmixture continued to stir for 24 hours at 25° C.Chlorodimethylsilylpropyloxy methacrylate (2.20 g, 0.01 mol) was thenadded and a color change was observed. Stirring was continued for 24hours more and the reaction mixture was then quenched with 10 mg NaHCO₃.Cyclohexane (10 mL) was added with continued stirring for 2 hours more.The reaction mixture was then filtered over Celite. The filtrate wasconcentrated under vacuum to give clear oil in 16 g yield as theexpected product M1-EDS9-TMS based on the method of preparation andcharacterized by NMR, SEC and MALDI.

Example 4 Synthesis of M1-EDS12-TMS

2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (19.2 g, 0.12 mol) wastaken in 50 mL of dry cyclohexane under N₂ and stirred for 30 minutes at25° C. To this mixture lithium trimethylsilanolate (960 mg, 0.01 mol)was added with stirring. After 2 hours dry THF (20 mL) was added and thereaction mixture continued to stir for 24 hours at 25° C.Chlorodimethylsilylpropyloxy methacrylate (2.20 g, 0.01 mol) was thenadded and a color change was observed. Stirring was continued for 24hours more and the reaction mixture was then filtered over Celite. Thefiltrate was concentrated under vacuum to give clear oil in 20 g yieldas the expected product M1-EDS12-TMS based on the method of preparationand characterized by NMR, SEC and MALDI.

Example 5 Synthesis of M1-EDS15-TMS

2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (24 g, 0.15 mol) wastaken in 60 mL of dry cyclohexane under N₂ and stirred for 10 minutes at25° C. To this lithium trimethylsilanolate (960 mg, 0.01 mol) was addedwith stirring. After 2 hours dry THF (20 mL) was added and the reactionmixture continued to stir for 24 hours at 25° C.Chlorodimethylsilylpropyloxy methacrylate (2.20 g, 0.01 mol) was thenadded and a color change was observed. Stirring was continued for 24hours more and the reaction mixture was then quenched with 10 mg NaHCO₃.Cyclohexane (10 mL) was added with continued stirring for 2 hours more.The reaction mixture was then filtered over Celite. The filtrate wasconcentrated under vacuum to give clear oil in 25 g yield as theexpected product M1-EDS15-TMS based on the method of preparation andcharacterized by NMR, SEC and MALDI.

Example 6 Synthesis of M1-BIS-EDS3-TMS

Lithium trimethyl silanolate (19.7 g, 0.2 mol) was suspended inanhydrous hexane (100 mL) in a 500 mL, round bottom flask was fittedwith a mechanical stirrer, argon gas and a dropping funnel. A solutionof 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (32.07 g, 0.2 mol)in anhydrous hexane (100 mL), was quickly added to the flask withstirring. After an hour, the flask was cooled with an ice bath and DMF(50 mL) was added with continued stirring. After 4 hours,3-methacryloxypropyl methyldichlorosilane (29 g, 0.12 mol) was addeddropwise to the reaction mixture. The reaction mixture was stirredfurther for 24 hours at room temperature. Deionized water (50 mL) wasthen added to the flask with stirring. The organic layer was separatedand dried over anhydrous sodium sulfate and filtered. The solvent wasevaporated on a rotovap to give the desired product M1-BIS-EDS3-TMS in40 g quantity as a clear, yellowish oil. The product was characterizedby GC, GC/MS, IR and NMR.

Example 7 Synthesis of Dimethylammonium Methacrylamide (MA1-Q-EDS9-TMS)

wherein n is 9.

2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (48 g, 0.3 mol) wastaken in 55 mL of dry cyclohexane under N₂ and stirred for 30 minutes at25° C. To this lithium trimethylsilanolate (4.8 g, 0.05 mol) was addedwith stirring. After 1 hour dry THF (25 mL) was added and the reactionmixture continued to stir for 24 hours at 25° C. Dimethylchlorosilane(5.1 g, 0.55 mol) was then added and a color change was observed.Stirring was continued for 3 hours more and the reaction mixture wasthen filtered. Filtrate was concentrated under vacuum to give clear oilin 42 g yield as the expected product based on the method of preparationand characterized by NMR, SEC and MALDI. 28.0 g of this was used forhydrosilation by taking into toluene (30 mL) and adding 1-bromobutene (4g, 0.03 mol,) under N₂ atmosphere followed by the addition ofplatinum(0)1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex 3 wt %solution in xylene (100 uL as catalyst). The reaction mixture wasstirred for 4 hours at 45-50° C. and then at 25° C. for 48 hours. Thereaction mixture was filtered over Celite using cotton plug. Strippingof the solvent on rotovap and then high vacuum to gave a yellow oil in27 g yield as the desired bromo compoundtrimethylsilyloxy-[poly(dimethylsilyl-ethyl-dimethylsilyloxy)]-dimethylsilylbutylbomidecharacterized by MALDI with n=˜9 units.

6.6 g (0.004 mol) of the bromo compound and 680 mg (0.004 mol) ofdimethylaminopropyl methacrylamide were mixed together and stirred underN₂ for 6 hours at 25° C. Some exotherm was observed. Reaction mixturewas subjected to high vacuum after 10 hours to give the desired productMA1-Q-EDS9-TMS in almost quantitative yield and characterized by NMR andMALDI.

Example 8 Synthesis of Comparative Monofunctional M1-MCR-C12

wherein n is 11.

Hydroxy ethoxypropyl terminated polydimethylsiloxane (50 grams, 0.048mol) available from Gelest, Inc. (MCR-C12) was added to a 500 mL roundbottom flask and dried via azeotropic distillation of toluene. To theflask was added anhydrous methylene chloride (200 mL) and triethylamine(17.12 g, 0.17 mol) and the reaction was stirred for 20 minutes. Thereaction flask was fitted with an addition funnel which was charged withmethacryloyl chloride (17.18 g, 0.16 mol) and an additional 85 mL ofanhydrous methylene chloride. The contents of the addition funnel wereadded to the reaction mixture dropwise at which time the addition funnelwas exchanged with a reflux condenser. The reaction was then brought toreflux for 4 hours. After cooling the reaction mixture was filtered andplaced in a separatory funnel where it was washed 2 times with 0.1 N HCl(150 mL); 2 times with sodium bicarbonate solution (150 mL) and 2 timeswith Brine solution (150 mL). The organic layer was then stirred with 10grams of decolorizing carbon and 10 grams of silica gel for 24 hours andwas then filtered and brought to dryness on a rotovap. The reactionyielded 45 g of a clear, yellow oil M1-MCR-C12 that was characterized byGC, NMR, and MALDI.

Example 9 Synthesis of Comparative Monofunctional MCA1-MCR-C12

wherein n is 11.

Hydroxy ethoxypropyl terminated polydimethylsiloxane (200 grams, 0.193mol) available from Gelest, Inc. (MCR-C12) was added to a 2 L roundbottom flask and dried via azeotropic distillation of toluene. To theflask was added anhydrous methylene chloride (500 mL) and dibutyltindilaurate (0.474 g, 0.0007 mol). The reaction flask was fitted with anaddition funnel which was charged with 2-Isocyanatoethyl methacrylate(45.0 g, 0.290 mol) and an additional 100 mL of anhydrous methylenechloride. The contents of the addition funnel was then added to thereaction mixture dropwise and the reaction was stirred for 48 hours. 50grams of silica gel (EMD Silica gel 60) was then added to the reactionmixture and stirred for 24 hours to scavenge excess isocyanatoethylmethacrylate. The reaction mixture was then filtered and concentrated ona rotovap yielding 210 g of a clear oil MCA1-MCR-C12 that wascharacterized by GC, NMR, and MALDI.

TABLE 1 Examples 10-23. Formulation of various EDS based monomers andcomparative examples Ma2D37 TRIS M1- MCa1- M1- Exam- Methacrylamide[tris(trimethylsiloxy)silylpropyl N-Vinyl N,N- 2-Hydroxyethyl MCR- MCR-EDS7- ple Crosslinker methacrylate] Pyrolidone Dimethylacrylamidemethacrylate Hexanol C12 C12 TMS 10 9.5 35.5 30.8 4.7 4.7 4.7 9.5 x x 119.5 35.5 30.8 4.7 4.7 4.7 x 9.5 x 12 9.5 35.5 30.8 4.7 4.7 4.7 x x 9.513 9.5 35.5 30.8 4.7 4.7 4.7 x x x 14 9.5 35.5 30.8 4.7 4.7 4.7 x x x 159.5 35.5 30.8 4.7 4.7 4.7 x x x 16 9.5 35.5 30.8 4.7 4.7 4.7 x x x 170.0 29.9 25.9 4.0 4.0 19.9 x x x 18 0.0 32.5 28.1 4.3 4.3 13.0 x x x 199.5 35.5 30.8 4.7 4.7 4.7 x x x 20 9.5 35.5 30.8 4.7 4.7 4.7 x x x 219.5 35.5 30.8 4.7 4.7 4.7 x x x 22 9.5 35.5 30.8 4.7 4.7 4.7 x x x 239.5 35.5 30.8 4.7 4.7 4.7 x x x M1- M1- M1- M1- M2- M1- M1- Ma1-Q- V1-VCa1- IMVT EDS6- EDS9- EDS12- EDS15- M2- D27- Bis- Bis-EDS3- EDS9- MCR-MCR- Darocur (concentration Example TMS TMS TMS TMS EDS23 EDS10 D3-TMSTMS TMS C12 C12 1173 in ppm) 10 x x x x x x x x x x x 0.47 90 11 x x x xx x x x x x x 0.47 90 12 x x x x x x x x x x x 0.47 90 13 9.5 x x x x xx x x x x 0.47 90 14 x 9.5 x x x x x x x x x 0.47 90 15 x x 9.5 x x x xx x x x 0.47 90 16 x x x 9.5 x x x x x x x 0.47 90 17 x 8.0 x x 8.0 x xx x x x 0.47 90 18 x 8.7 x x x 8.7 x x x x x 0.47 90 19 x x x x x x 9.5x x x x 0.47 90 20 x x x x x x x 9.5 x x x 0.47 90 21 x x x x x x x x9.5 x x 0.47 90 22 x x x x x x x x x 9.5 x 0.47 90 23 x x x x x x x x xx 9.5 0.47 90 Note: The amounts presented in the table above are weightpercentages in the formulation. Tint level is in ppm.

Preparation Procedure:

For examples 10-15, 17-23, 32, 54-56, 69 and 70, the specific monomermixes set forth were prepared according to the table 1 above and tables3, 5 and 6 below by weighing out various weight percentages of thecomponents. Monomer mix was dispensed between polypropylene molds andprepared as lenses or flats in the case of Dk samples. Polymerizationwas carried out under UV light (˜350 nm) for a period of two hours.After polymerization, the lenses or flats were released from the moldsusing 33% IPA in water and then extracted in 100% IPA for 4 hours.Lenses/Flats were then placed in deionized water for 30 minutes andpackaged in vials containing 4 mL of borate buffered saline (BBS).Measured properties for the lenses/flats are shown in the table below.

TABLE 2 Selected Characteristics of processed lenses/flats containingEDS monomers and comparative examples. Water Dk Modulus Elongation TearStrength Advancing Receding Example Content (%) (barrers) (gm/sqmm) (%)(gm/mm) Contact Angle Contact Angle Hysteressis 10 42.3 96  92 (10) 125(52) 7 (1) 28 (4) 19 (0) 9 (4) 11 43.0 x 107 (10) 100 (30) 4 (1) 29 (2)21 (1) 8 (1) 12 47.3 93 58 (6) 100 (30) 4 (1) 29 (2) 21 (1) 8 (1) 1340.8 87 91 (9) 177 (25) 5 (1) 29 (3) 21 (3) 8 (6) 14 42.1 x .3/17 .3/17.3/17 x x x 15 35.7 x .3/17 .3/17 .3/17 x x x 17 42.0 95 74 (4) 236 (25)7 (1) x x x 18 41.6 85 66 (5) 143 (43) 6 (1) 19 40.9 x 137 (6)  157 (22)x x x x 20 32.0 x 137 (8)  137 (20) x x x x 21 43.1 x 140 (6)   96 (14)x x x x 22 41.9 x  98 (10) 159 (29)   6 (0.4) 98 (2) 21 (1) 76 (1) 2339.2 x 105 (5)  125 (23) 5 (1) 96 (5) 21 (1) 76 (5) 32 46.9 91 71 (8)165 (74) x 31 (6) 16 (1) 15 (5) 54 44.9 x  84 (10) 177 (31) 4 (1)   33(0.7)   19 (1.0)   14 (1.6) 55 43.2 x 80 (7) 176 (60) 7 (1)   40 (7.0)  24 (2.3)   16 (9.2) 56 43.3 x 72 (4) 159 (68)   7 (0.3)   41 (2.0)  22 (1.4)   19 (0.6) 69 32.0 x 137 (8)  137 (20) x x x x 70 43 85 77(6) 200 (24)   5 (0.2)   39 (9.7)   22 (1.5)   17 (10.9)

A 4502 Mechanical Tester MTS Instron was used to measure the modulus,tensile strength, percent elongation and tear strength of the lenses.Samples were tested in a water bath containing borate buffered saline.

Captive bubble contact angle data was collected on a First Ten AngstromsFTA-1000 Drop Shape Instrument. All samples were rinsed in HPLC gradewater prior to analysis in order to remove components of the packagingsolution from the sample surface. Prior to data collection the surfacetension of the water used for all experiments was measured using thependant drop method. In order for the water to qualify as appropriatefor use, a surface tension value of 70-72 dynes/cm was expected. Alllens samples were placed onto a curved sample holder and submerged intoa quartz cell filled with HPLC grade water. Receding and advancingcaptive bubble contact angles were collected for each sample. Thereceding contact angle is defined as the angle measured in water as theair bubble is expanding across the sample surface (water is recedingfrom the surface). The advancing contact angle is defined as the anglemeasured in water as the air bubble is retracting from the lens surface(water is advancing across the surface). All captive bubble data wascollected using a high speed digital camera focused onto the sample/airbubble interface. The contact angle was calculated at the digital framejust prior to contact line movement across the sample/air bubbleinterface.

TABLE 3 Further examples of monomer mix formulations. Ma2D37 TRIS M1-IMVT Methacrylamide [tris(trimethylsiloxy)- N-Vinyl N,N- 2-HydroxyethylEDS6- Darocur (concentration Example Crosslinker silylpropylmethacrylate] Pyrolidone Dimethylacrylamide methacrylate Hexanol TMS1173 in ppm) 24 0.1 41.2 58.1 0.0 0.0 0.0 0.1 0.48 90 25 4.7 38.4 29.21.9 7.6 4.4 13.3 0.47 90 26 7.0 30.5 20.5 3.0 7.0 4.7 27.0 0.48 90 2711.1 29.4 27.7 2.6 6.0 4.0 18.8 0.43 90 28 32.3 28.0 13.8 4.3 4.3 4.012.9 0.43 90 29 44.7 12.9 23.0 0.0 4.2 3.9 10.9 0.42 90 30 59.7 9.6 14.30.0 4.8 4.5 6.7 0.48 90 31 75.8 0.0 0.0 9.5 9.5 4.7 0.1 0.47 90 32 6.635.5 30.8 4.7 4.7 4.7 12.3 0.47 90 33 4.5 9.0 58.8 4.5 0.0 13.6 9.1 0.4590 34 6.1 18.2 18.2 1.2 1.2 48.6 6.1 0.30 90 35 7.7 23.1 23.1 1.5 1.534.6 7.7 0.48 90 36 15.9 15.9 23.9 4.0 4.0 19.9 15.9 0.40 90 37 5.0 10.029.9 5.0 5.0 14.9 29.9 0.50 90 Note: The amounts presented in the tableabove are weight percentages in the formulation. Tint level is in ppm.

TABLE 4 Further examples of monomer mix formulations. TRIS Ma2D37[tris(trimethylsiloxy)- M1- IMVT Methacrylamide silylpropyl N-Vinyl N,N-2-Hydroxyethyl EDS6- Darocur (concentration Example Crosslinkermethacrylate] Pyrolidone Dimethylacrylamide methacrylate Hexanol TMS1173 in ppm) 38 0.1 41.2 58.1 0.0 0.0 0.0 0.1 0.48 145 39 4.7 38.4 29.21.9 7.6 4.4 13.3 0.47 145 40 7.0 30.5 20.5 3.0 7.0 4.7 27.0 0.48 145 4111.1 29.4 27.7 2.6 6.0 4.0 18.8 0.43 145 42 32.3 28.0 13.8 4.3 4.3 4.012.9 0.43 145 43 44.7 12.9 23.0 0.0 4.2 3.9 10.9 0.42 145 44 59.7 9.614.3 0.0 4.8 4.5 6.7 0.48 145 45 75.8 0.0 0.0 9.5 9.5 4.7 0.1 0.47 14546 6.6 35.5 30.8 4.7 4.7 4.7 12.3 0.47 145 47 4.5 9.0 58.8 4.5 0.0 13.69.1 0.45 145 48 6.1 18.2 18.2 1.2 1.2 48.6 6.1 0.30 145 49 7.7 23.1 23.11.5 1.5 34.6 7.7 0.48 145 50 15.9 15.9 23.9 4.0 4.0 19.9 15.9 0.40 14551 5.0 10.0 29.9 5.0 5.0 14.9 29.9 0.50 145 Note: The amounts presentedin the table above are weight percentages in the formulation. Tint levelis in ppm.

TABLE 5 Further examples of monomer mix formulations. TRIS Ma2D37[tris(trimethylsiloxy)- Methacrylamide silylpropyl N-Vinyl N,N-2-Hydroxyethyl Example Crosslinker methacrylate] PyrolidoneDimethylacrylamide methacrylate 52 0.1 41.2 58.1 0.0 0.0 53 4.7 38.429.2 1.9 7.6 54 6.6 35.6 30.8 4.7 4.7 55 6.6 35.6 30.8 4.7 4.7 56 6.635.6 30.8 4.7 4.7 57 7.0 30.5 20.5 3.0 7.0 58 11.1 29.4 27.7 2.6 6.0 5932.3 28.0 13.8 4.3 4.3 60 44.7 12.9 23.0 0.0 4.4 61 59.7 9.6 14.3 0.04.8 62 75.8 0.0 0.0 9.5 9.5 63 6.6 35.5 30.8 4.7 4.7 64 4.5 9.0 58.8 4.50.0 65 6.1 18.2 18.2 1.2 1.2 66 7.7 23.1 23.1 1.5 1.5 67 15.9 15.9 23.94.0 4.0 68 5.0 10.0 29.9 5.0 5.0 69 9.5 35.5 30.8 4.7 4.7 M1- M1-BIS-IMVT t-Amyl EDS6- EDS3- Darocur (concentration Example Hexanol Nonanolalcohol TMS TMS 1173 in ppm) 52 0.0 5.1 0.0 0.1 0.0 0.1 200 53 4.4 4.40.0 13.3 0.0 0.47 200 54 4.7 0.0 0.0 12.3 0.0 0.47 200 55 0.0 4.7 0.012.3 0.0 0.47 200 56 0.0 0.0 4.7 12.3 0.0 0.47 200 57 0.0 4.7 0.0 27.00.0 0.48 200 58 4.0 0.0 0.0 18.8 0.0 0.43 200 59 0.0 0.0 4.0 12.9 0.00.43 200 60 0.0 3.9 0.0 10.9 0.0 0.2 200 61 0.0 0.0 4.5 6.7 0.0 0.48 20062 4.7 0.0 0.0 0.1 0.0 0.47 200 63 4.7 0.0 0.0 12.3 0.0 0.47 200 64 0.013.6 0.0 9.1 0.0 0.45 200 65 0.0 0.0 48.6 6.1 0.0 0.30 200 66 34.6 0.00.0 7.7 0.0 0.48 200 67 0.0 19.9 0.0 15.9 0.0 0.40 200 68 0.0 0.0 14.929.9 0.0 0.50 200 69 4.7 4.7 0.0 0.0 9.5 0.47 60 Note: The amountspresented in the table above are weight percentages in the formulation.Tint level is in ppm.

TABLE 6 Further examples of monomer mix formulations. Ma2D37 TRISMethacrylamide [tris(trimethylsiloxy)silylpropyl N-Vinyl N,N-2-Hydroxyethyl Example Crosslinker methacrylate] PyrolidoneDimethylacrylamide methacrylate 70 7.0 34.6 30.6 4.7 4.7 71 9.5 35.535.3 7.7 4.7 72 0.1 41.2 58.1 0.0 0.0 73 4.7 38.4 29.2 1.9 7.6 74 6.635.6 30.8 4.7 4.7 75 6.6 35.6 30.8 4.7 4.7 76 6.6 35.6 30.8 4.7 4.7 777.0 30.5 20.5 3.0 7.0 78 11.1 29.4 27.7 2.6 6.0 79 32.3 28.0 13.8 4.34.3 80 44.7 12.9 23.0 0.0 4.4 81 59.7 9.6 14.3 0.0 4.8 82 75.8 0.0 0.09.5 9.5 83 6.6 35.5 30.8 4.7 4.7 84 4.5 9.0 58.8 4.5 0.0 85 6.1 18.218.2 1.2 1.2 86 7.7 23.1 23.1 1.5 1.5 IMVT t-Amyl M1-EDS6- SA Irgacure(concentration Example Hexanol Nonanol alcohol TMS Monomer 819 in ppm)70 0.0 4.7 0.0 12.6 0.6 0.5 200 71 4.7 4.7 0.0 0.0 2.0 0.47 200 72 0.05.1 0.0 0.1 0.5 0.1 200 73 4.4 4.4 0.0 13.3 1.1 0.47 200 74 4.7 0.0 0.012.3 0.0 0.47 200 75 0.0 4.7 0.0 12.3 0.0 0.47 200 76 0.0 0.0 4.7 12.30.0 0.47 200 77 0.0 4.7 0.0 27.0 0.0 0.48 200 78 4.0 0.0 0.0 18.8 0.00.43 200 79 0.0 0.0 4.0 12.9 0.0 0.43 200 80 0.0 3.9 0.0 10.9 0.0 0.2200 81 0.0 0.0 4.5 6.7 0.0 0.48 200 82 4.7 0.0 0.0 0.1 0.0 0.47 200 834.7 0.0 0.0 12.3 0.0 0.47 200 84 0.0 13.6 0.0 9.1 0.0 0.45 200 85 0.00.0 48.6 6.1 0.0 0.30 200 86 34.6 0.0 0.0 7.7 0.0 0.48 200 Note: Theamounts presented in the table above are weight percentages in theformulation. Tint level is in ppm.

Example 87 Capping of EDS withchlorodimethyl(3-(2,2,3,3,4,4,5,5-octafluoropentyloxy)propyl)silane StepI

Substance Amount Dimethylchlorosilane 120 mL Allylloxyoctafluoropentane200 g Pt/Si catalyst 640 μL Anhydrous toluene 250 mL Anhydroustetrahydrofuran 250 mL

In a 1000 mL three-neck round bottom flask fitted with a refluxcondenser, thermo-controller, magnetic stirrer and Argon gas blanket, amixture of dimethylchlorosilane, toluene and THF was added to the flask.Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyl disiloxane was then added.The flask was heated to 60° C. for 7 hours. The reaction mixtureexothermed at about 85° C. after about a half hour. A sample waswithdrawn from the flask and checked by GC and showed a little startingmaterial. The reaction was continued to run for about seven hours. Thechlorodimethyl(3-(2,2,3,3,4,4,5,5-octafluoropentyloxy)propyl)silane wasvacuum distilled at 70-80° C.

Step II

Deionized water (100 mL) and diethyl ether (200 mL) were added to asingle-neck 500 mL round-bottom flask fitted with a magnetic stirrer.The flask was cooled in an ice bath to 0° C. The flask was fitted with adropping funnel and a mixture of (10 g, 0.045 mol) of3-methacryloxypropyl dimethylchlorosilane and 50 mL of anhydrous THF wasadded to the flask. The reaction was stirred for one hour at 0° C. Theorganic layer was separated and dried over anhydrous sodium sulfate andfiltered. The solvent was evaporated on a rotovap to give3-methacryloxypropyl dimethylhydroxysilane in 9.0 g quantity, 99% yieldas a clear, colorless oil.

The 3-methacryloxypropyl dimethylhydroxysilane (4 g, 0.02 mol) was addedto a single-neck 500 mL round-bottom flask fitted with a magneticstirrer. A 2.5 M n-BuLi (0.006 mol) mixture was slowly added to theflask. A mixture of 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane(65.3 g, 0.4 mol) and THF (50 mL) was added to the flask. The reactionstirred for 24 h. Thechlorodimethyl(3-(2,2,3,3,4,4,5,5-octafluoropentyloxy)propyl)silane (7.1g, 0.02 mol) was added to the flask and stirred for 24 h. The solventwas evaporated on a rotovap to give3-methacryloxypropyldimethylsilyloxy-EDS10-dimethylsilylpropyloxyoctafluoropentanein 38 g quantity, 90% yield as a clear, colorless oil. The sample waschecked by NMR spectroscopy, GC-MS and MALDI.

Example 88 Ring Opening of EDS withchlorodimethyl(3-(2,2,3,3,4,4,5,5-octafluoropentyloxy)propyl)silane

Step I

In a 250 mL one-neck round bottom flask fitted with a magnetic stirrerunder nitrogen gas in an ice bath, water and ether were added andstirred.Chlorodimethyl(3-(2,2,3,3,4,4,5,5-octafluoropentyloxy)propyl)silane andTHF was added to a dropping funnel and added dropwise to the water/ethermixture. The reaction was stirred at 0° C. for one hour. The productmixture was extracted with ether, dried with sodium sulfate, filteredand the ether was rotovapped off. The3-dimethyl(3-(2,2,3,3,4,4,5,5-octafluoropentyloxy)propyl)silanol productwas used in the next step of the reaction.

Step II

In a 500 mL, round bottom flask, fitted with a mechanical stirrer, Argas and a dropping funnel;3-dimethyl(3-(2,2,3,3,4,4,5,5-octafluoropentyloxy)propyl)silanol product(7 g, 0.02 mol) was added. A 2.5 M n-BuLi (0.006 mol) mixture was slowlyadded to the flask followed by the addition of a solution of2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (65 g, 0.4 mol) in THF(50 mL). The reaction was continued to stir for 24 hours.3-(chlorodimethylsilyl)propyl methacrylate (4.84 g, 0.022 mol) was addedto the reaction mixture and the stirring was further continued for 6hours. After that solvent was evaporated under vacuum to afford theproduct that was characterized by NMR and MALDI.

Example 89 Improved Lubricity by Coating with Phosphoryl Choline

For each sample, a 0.5% solution in BBS was prepared by adding 1.25 g ofpolymer to BBS. The total volume of the solution was 250 mL. The pH ofthe solutions was 7.2. The test solution was poly(phosphocholine).Comparative solutions comprising separately Poly(acrylic acid)—450,000g/mol, Tetronic T1107, Tetronic T908, HPMC or Polymer JR were alsoprepared. All solutions were made at a concentration of 0.5% in BBS andpH was adjusted to 7.2 if needed (by standard techniques known in theart). For lens testing, 4.5 mL of each solution was added to a glassautoclave vial. An organosilicon-containing lens was placed in each vialand the system was capped with a Teflon-coated crimp cap. Each systemwas then autoclaved (121° C. for 30 minutes). The packaged lens was thenremoved from the package and rinsed with DI water. The rinsed lens wasthen placed on a polystyrene Petri dish and sectioned with a scalpel inorder to cause the lens to lie flat.

Preferred Embodiments

Disclosed in certain preferred embodiments of the invention herein is:1. A monomer having a structural formula (I):

wherein X is the residue of a ring opening agent or a capping agent; Lis the same or different and is a linker group or a bond; V is anethylenically unsaturated polymerizable group; R₁, R₂, R₃, R₄, R₅, R₆are independently H, alkyl, halo alkyl, heteroalkyl, cyclo alkyl,heterocyclo alkyl, alkenyl, halo alkenyl, or aromatic; R₇ and R₈ whenpresent are independently H or alkyl wherein at least one of R₇ or R₈ ishydrogen; y is 2-7 and n is 1-100.2. A monomer having a structural formula (II)

wherein L is the same or different and is a linker group or a bond and Vis the same or different and is an ethylenically unsaturatedpolymerizable group, R₁, R₂, R₃, R₄, R₅, R₆ and R₉ are independently H,alkyl, halo alkyl, cyclo alkyl, heterocyclo alkyl, alkenyl, haloalkenyl, or aromatic, R₇ and R₈ are independently H or alkyl wherein atleast one of R₇ or R₈ is hydrogen, y is 2-7 and n is 1-100.3. A monomer according to preferred embodiment 1 wherein the X is aresidue of a ring opening agent selected from the group consisting ofalkyl lithiums, alkoxides, trialkylsiloxylithiums and acrylicester-capped polysiloxane prepolymers in the presence of an acidcatalyst.4. The monomer of preferred embodiment 3 wherein the residue of the ringopening agent contains halo atoms.5. The monomer of preferred embodiment 1 wherein linker group isselected from the group consisting of substituted or unsubstitutedalkyl, alkyl ether, alkenyls, alkenyl ethers, halo alkyls, substitutedor unsubstituted siloxanes, and monomers capable of propagating ringopening.6. The monomer of preferred embodiment 2 wherein linker group isselected from the group consisting of substituted or unsubstitutedalkyl, alkyl ether, alkenyls, alkenyl ethers, halo alkyls, substitutedor unsubstituted siloxanes, and monomers capable of propagating ringopening.7. The monomer of preferred embodiment 1 having a structural formula(III):

wherein R₉, R₁₀ and R₁₁ are independently H, alkyl, haloalkyl or othersubstituted alkyl groups, n is 1-100 and n¹ is 0-10.8. The monomer of preferred embodiment 1 having a structural formula(IV):

wherein n is 1-100.9. The monomer of preferred embodiment 8 wherein n is 2-80.10. The monomer of preferred embodiment 8 wherein n is 3-20.11. The monomer of preferred embodiment 8 wherein n is 5-15.12. A monomer of preferred embodiment 1 wherein V is selected from thegroup consisting of acrylates, methacrylates, vinyl carbonates, O-vinylcarbamates, N-vinyl carbamates, acrylamides and methacrylamides.13. A monomer of preferred embodiment 2 wherein V is selected from thegroup consisting of acrylates, methacrylates, vinyl carbonates, O-vinylcarbamates, N-vinyl carbamates, acrylamides and methacrylamides.14. The monomer of preferred embodiment 1 having a structural formulaselected from the group consisting of the following structural formulae:

15. The monomer of preferred embodiment 1 having a structural formulaselected from the group consisting of the following structural formulae:

wherein R₉, R₁₀ and R₁₁ are independently H, alkyl, haloalkyl or othersubstituted alkyl groups and n is 1-100 and n¹ is 0-10.16. The monomer of preferred embodiment 1 having a structural formulaselected from the group consisting of the following structural formulae:

wherein n is 1-100 and X⁻ is a counterion to provide an overall neutralcharge.17. The monomer of preferred embodiment 1 having the followingstructural formula:

18. A monomer mix useful for forming a medical device wherein themonomer mix comprises at least one monomer selected from the groupconsisting of the monomers of preferred embodiment 1 and whenpolymerized forms a medical device.19. A monomer mix useful for forming a medical device wherein themonomer mix comprises at least one monomer selected from the groupconsisting of the monomers of preferred embodiment 2 and whenpolymerized forms a medical device.20. The monomer mix of preferred embodiment 18 further comprising asecond copolymerizable second monomer.21. The monomer mix of preferred embodiment 19 further comprising asecond copolymerizable second monomer.22. The monomer mix of preferred embodiment 18 wherein the medicaldevice formed is selected from the group consisting of rigid contactlenses, soft contact lenses, phakic intraocular lenses, aphakicintraocular lenses and corneal implants.23. The monomer mix of preferred embodiment 19 wherein the medicaldevice formed is selected from the group consisting of rigid contactlenses, soft contact lenses, phakic intraocular lenses, aphakicintraocular lenses and corneal implants.24. The monomer mix of preferred embodiment 18 wherein the medicaldevice formed is selected from the group consisting of artificial heartvalves, films, surgical devices, vessel substitutes, intrauterinedevices, membranes, diaphragms, surgical implants, artificial bloodvessels, artificial ureters, artificial breast tissue, membranesintended to come into contact with body fluid outside of the body,membranes for kidney dialysis machines, membranes for heart/lungmachines, catheters, mouth guards, denture liners, ophthalmic devices,and hydrogel contact lenses.25. The monomer mix of preferred embodiment 19 wherein the medicaldevice formed is selected from the group consisting of artificial heartvalves, films, surgical devices, vessel substitutes, intrauterinedevices, membranes, diaphragms, surgical implants, artificial bloodvessels, artificial ureters, artificial breast tissue, membranesintended to come into contact with body fluid outside of the body,membranes for kidney dialysis machines, membranes for heart/lungmachines, catheters, mouth guards, denture liners, ophthalmic devices,and hydrogel contact lenses.26. The monomer mix of preferred embodiment 24 wherein the medicaldevice is a hydrogel contact lens.

27. The monomer mix of preferred embodiment 25 wherein the medicaldevice is a hydrogel contact lens.

28. The monomer mix of preferred embodiment 18 wherein the at least onemonomer selected from the group consisting of the monomers of preferredembodiment 1 is an mono ethylenically unsaturated polymerizable groupcontaining polycarbosiloxane monomer.

29. The monomer mix of preferred embodiment 19 wherein the at least onemonomer selected from the group consisting of the monomers of preferredembodiment 2 is an mono ethylenically unsaturated polymerizable groupcontaining polycarbosiloxane monomer.30. The monomer mix of preferred embodiment 28 wherein the monoethylenically unsaturated polymerizable group containingpolycarbosiloxane monomer is present in an amount from about 0.1 toabout 30 percent by weight of the monomer mix.31. The monomer mix of preferred embodiment 28 wherein the monoethylenically unsaturated polymerizable group containingpolycarbosiloxane monomer is present in an amount from about 0.1 toabout 20 percent by weight of the monomer mix.32. The monomer mix of preferred embodiment 28 wherein the monoethylenically unsaturated polymerizable group containingpolycarbosiloxane monomer is present in an amount from about 5 to about15 percent by weight of the monomer mix.33. The monomer mix of preferred embodiment 29 wherein the monoethylenically unsaturated polymerizable group containingpolycarbosiloxane monomer is present in an amount from about 0.1 toabout 30 percent by weight of the monomer mix.34. The monomer mix of preferred embodiment 29 wherein the monoethylenically unsaturated polymerizable group containingpolycarbosiloxane monomer is present in an amount from about 0.1 toabout 20 percent by weight of the monomer mix.35. The monomer mix of preferred embodiment 29 wherein the monoethylenically unsaturated polymerizable group containingpolycarbosiloxane monomer is present in an amount from about 5 to about15 percent by weight of the monomer mix.36. The monomer mix of preferred embodiment 20 wherein the secondcopolymerizable second monomer is a hydrophobic silicone containingmonomer.37. The monomer mix of preferred embodiment 36 wherein the hydrophobicsilicone containing monomer is present in the monomer mix between about0.1 to about 75.8 percent by weight.38. The monomer mix of preferred embodiment 36 wherein the hydrophobicsilicone containing monomer is present in the monomer mix between about2 to about 20 percent by weight.39. The monomer mix of preferred embodiment 36 wherein the hydrophobicsilicone containing monomer is present in the monomer mix between about5 to about 13 percent by weight.40. The monomer mix of preferred embodiment 21 wherein the secondcopolymerizable second monomer is a hydrophobic silicone containingmonomer.41. The monomer mix of preferred embodiment 40 wherein the hydrophobicsilicone containing monomer is present in the monomer mix between about0.1 to about 75.8 percent by weight.42. The monomer mix of preferred embodiment 40 wherein the hydrophobicsilicone containing monomer is present in the monomer mix between about2 to about 20 percent by weight.43. The monomer mix of preferred embodiment 40 wherein the hydrophobicsilicone containing monomer is present in the monomer mix between about5 to about 13 percent by weight.44. The monomer mix of preferred embodiment 20 wherein the secondcopolymerizable monomer is a non-silicone containing hydrophobicmonomer.45. The monomer mix of preferred embodiment 21 wherein the secondcopolymerizable monomer is a non-silicone containing hydrophobicmonomer.46. The monomer mix of preferred embodiment 20 wherein the non-siliconecontaining hydrophobic monomer is present at about 0 to about 60 percentby weight.47. The monomer mix of preferred embodiment 21 wherein the non-siliconecontaining hydrophobic monomer is present at about 0 to about 60 percentby weight.48. The monomer mix of preferred embodiment 20 wherein the non-siliconecontaining hydrophobic monomer is selected from the group consisting ofalkyl acrylates and alkyl methacrylates.49. The monomer mix of preferred embodiment 21 wherein the non-siliconecontaining hydrophobic monomer is selected from the group consisting ofalkyl acrylates and alkyl methacrylates.50. The monomer mix of preferred embodiment 20 wherein the secondcopolymerizable monomer is a bulky monomers selected from the groupconsisting of methacryloxypropyl tris(trimethylsiloxy)silane (“TRIS”),pentamethyldisiloxanyl methylmethacrylate,tris(trimethylsiloxy)methacryloxy propylsilane,phenyltretramethyl-disloxanylethyl acrylate,methyldi(trimethylsiloxy)methacryloxymethyl silane,3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate,3[tris(trimethylsiloxy)silyl]propyol allyl carbamate, and3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate.51. The monomer mix of preferred embodiment 21 wherein the secondcopolymerizable monomer is a bulky monomers selected from the groupconsisting of methacryloxypropyl tris(trimethylsiloxy)silane (“TRIS”),pentamethyldisiloxanyl methylmethacrylate,tris(trimethylsiloxy)methacryloxy propylsilane,phenyltretramethyl-disloxanylethyl acrylate,methyldi(trimethylsiloxy)methacryloxymethyl silane,3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate,3[tris(trimethylsiloxy)silyl]propyol allyl carbamate, and3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate.52. The monomer mix of preferred embodiment 50 wherein the bulky monomeris present at about 0 to about 41.2 percent by weight.53. The monomer mix of preferred embodiment 50 wherein the bulky monomeris present at about 34 to about 41 percent by weight.54. The monomer mix of preferred embodiment 50 wherein the bulky monomeris present at about 25 to about 41 percent by weight.55. The monomer mix of preferred embodiment 51 wherein the bulky monomeris present at about 0 to about 41.2 percent by weight.56. The monomer mix of preferred embodiment 51 wherein the bulky monomeris present at about 34 to about 41 percent by weight.57. The monomer mix of preferred embodiment 51 wherein the bulky monomeris present at about 25 to about 41 percent by weight.58. The monomer mix of preferred embodiment 26 wherein the monomer mixcomprises a mixture containing at least one silicone-containing monomerand at least one hydrophilic monomer.59. The monomer mix of preferred embodiment 26 wherein the monomer mixcomprises a separate crosslinker.60. The monomer mix of preferred embodiment 59 wherein the separatecrosslinker is selected from the group consisting of methacrylates,ethylene glycol dimethacrylate (EGDMA) and allyl methacrylate (AMA).61. The monomer mix of preferred embodiment 60 wherein the separatecrosslinker is present at between about 0 to about 76 percent by weight.62. The monomer mix of preferred embodiment 60 wherein the separatecrosslinker is present at between about 2 to about 20 percent by weight.63. The monomer mix of preferred embodiment 60 wherein the separatecrosslinker is present at between about 5 to about 13 percent by weight.64. The monomer mix of preferred embodiment 27 wherein thesilicone-containing monomer is a crosslinking agent.65. The monomer mix of preferred embodiment 20 wherein the secondcopolymerizable monomer is a hydrophilic monomer.66. The monomer mix of preferred embodiment 65 wherein the hydrophilicmonomer is selected from the group consisting of unsaturated carboxylicacids, methacrylic acids, acrylic acids; acrylic substituted alcohols,2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate; vinyl lactams,N-vinylpyrrolidone (NVP), 1-vinylazonan-2-one; acrylamides,methacrylamide, N,N-dimethylacrylamide (DMA) and mixtures thereof.67. The monomer mix of preferred embodiment 65 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts ofbetween about 0 to about 60 percent by weight.68. The monomer mix of preferred embodiment 65 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts betweenabout 20 to about 45 percent by weight.69. The monomer mix of preferred embodiment 65 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts betweenabout 0 to about 48.6 percent by weight.70. The monomer mix of preferred embodiment 65 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts betweenabout 0 to about 30 percent by weight.71. The monomer mix of preferred embodiment 65 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts betweenabout 0 to about 25 percent by weight.72. The monomer mix of preferred embodiment 65 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts betweenabout 0 to about 9.5 percent by weight.73. The monomer mix of preferred embodiment 65 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts betweenabout 2 to about 7 percent by weight.74. The monomer mix of preferred embodiment 21 wherein the secondcopolymerizable monomer is a hydrophilic monomer.75. The monomer mix of preferred embodiment 74 wherein the hydrophilicmonomer is selected from the group consisting of unsaturated carboxylicacids, methacrylic acids, acrylic acids; acrylic substituted alcohols,2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate; vinyl lactams,N-vinylpyrrolidone (NVP), 1-vinylazonan-2-one; acrylamides,methacrylamide, N,N-dimethylacrylamide (DMA) and mixtures thereof.76. The monomer mix of preferred embodiment 74 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts ofbetween about 0 to about 60 percent by weight.77. The monomer mix of preferred embodiment 74 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts betweenabout 20 to about 45 percent by weight.78. The monomer mix of preferred embodiment 74 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts betweenabout 0 to about 48.6 percent by weight.79. The monomer mix of preferred embodiment 74 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts betweenabout 0 to about 30 percent by weight.80. The monomer mix of preferred embodiment 74 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts betweenabout 0 to about 25 percent by weight.81. The monomer mix of preferred embodiment 74 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts betweenabout 0 to about 9.5 percent by weight.82. The monomer mix of preferred embodiment 74 wherein the hydrophilicmonomer is present, separately or by combined weight in amounts betweenabout 2 to about 7 percent by weight.83. The monomer mix of preferred embodiment 36 further comprising anorganic diluent.84. The monomer mix of preferred embodiment 83 wherein the organicdiluent is selected from the group consisting of alcohols, tert-butanol(TBA), tert-amyl alcohol, hexanol and nonanol; diols, ethylene glycol;polyols, glycerol and mixtures thereof.85. The monomer mix of preferred embodiment 83 wherein the organicdiluent is present at about 0 to about 60% by weight of the monomericmixture.86. The monomer mix of preferred embodiment 83 wherein the organicdiluent is present at about 1 to about 40% by weight.87. The monomer mix of preferred embodiment 83 wherein the organicdiluent is present at about 2 to about 30% by weight.88. The monomer mix of preferred embodiment 83 wherein the organicdiluent is present at about 3 to about 25% by weight.89. The monomer mix of preferred embodiment 40 further comprising anorganic diluent.90. The monomer mix of preferred embodiment 89 wherein the organicdiluent is selected from the group consisting of alcohols, tert-butanol(TBA), tert-amyl alcohol, hexanol and nonanol; diols, ethylene glycol;polyols, glycerol and mixtures thereof.91. The monomer mix of preferred embodiment 89 wherein the organicdiluent is present at about 0 to about 60% by weight of the monomericmixture.92. The monomer mix of preferred embodiment 89 wherein the organicdiluent is present at about 1 to about 40% by weight.93. The monomer mix of preferred embodiment 89 wherein the organicdiluent is present at about 2 to about 30% by weight.94. The monomer mix of preferred embodiment 89 wherein the organicdiluent is present at about 3 to about 25% by weight.95. A hydrogel contact lens comprising a polymerized monomer mixcomprising a polymerizable monomer mixture comprising about 0.1 to about75.8 percent by weight of a methacrylamide crosslinker, about 0 to about41.2 percent by weight of a bulky siloxane monomer, about 0 to about 78percent by weight of at least one hydrophilic monomer, about 0 to about48.6 percent by weight of an alcohol, about 0.1 to about 29.9 weightpercent of an mono ethylenically unsaturated polymerizable groupcontaining polycarbosiloxane monomer, about 0.1 to about 1.0 percent byweight of an initiator and about 90 to about 200 parts per million of avisibility tint.96. The hydrogel contact lens of preferred embodiment 95 comprising aspart of polymerizable monomer mixture comprising about 5 to about 13percent by weight of a methacrylamide crosslinker, about 34 to about 41percent by weight of a bulky siloxane monomer, about 28 to about 52percent by weight of at least one hydrophilic monomer, about 0 to about25 percent by weight of an alcohol, about 5 to about 15 weight percentof an mono ethylenically unsaturated polymerizable group containingpolycarbosiloxane monomer, about 0.2 to about 0.8 percent by weight ofan initiator and about 90 to about 145 parts per million of a visibilitytint.97. The hydrogel contact lens of preferred embodiment 95 comprising aspart of polymerizable monomer mixture comprising about 2 to about 8percent by weight of a methacrylamide crosslinker, about 25 to about 38percent by weight of a bulky siloxane monomer, about 35 to about 45percent by weight of at least one hydrophilic monomer, about 3 to about8 percent by weight of an alcohol, about 10 to about 13 weight percentof an mono ethylenically unsaturated polymerizable group containingpolycarbosiloxane monomer, about 0.3 to about 0.6 percent by weight ofan initiator and about 145 to about 200 parts per million of avisibility tint.98. A monomer mix useful for forming a medical device wherein themonomer mix comprises at least one monomer selected from the groupconsisting of any one of the monomers of preferred embodiments 1-17 andwhen polymerized forms an ophthalmic medical device to be implanted inor on an eye.99. A medical device comprising a polymerized monomer mix of any one ofembodiments 18-94.100. The medical device of embodiment 99 wherein the medical device iscoated with a polymer comprising at least one of the following monomers:HEMA, glyceryl methacrylate, methacrylic acid (“MAA”), acrylic acid(“AA”), methacrylamide, acrylamide, N,N′-dimethylmethacrylamide, orN,N′-dimethylacrylamide; copolymers thereof; hydrophilic prepolymers,such as ethylenically unsaturated poly(alkylene oxide)s, cyclic lactamssuch as N-vinyl-2-pyrrolidone (“NVP”), vinyl carbonate or vinylcarbamate monomers.101. A method of making a medical device comprising providing a monomermix which comprises at least one monomer selected from the groupconsisting of any one of the monomers of preferred embodiments 1-17 in amold suitable for forming a medical device and exposing the moldcontaining the monomer mix to at least visible light at a sufficientintensity and for a sufficient period of time such that the monomer mixis polymerized and forms an ophthalmic medical device to be implanted inor on an eye.102. A hydrogel contact lens system comprising a polymerized monomermixture of any one of the monomer mixes of embodiments 18-94 placed in apackage which comprises a flange with a well formed therein for holdinga contact lens in solution, a flexible cover sheet which extends overthe flange and is sealed about the perimeter of the well to seal thelens and solution in the well wherein the package has at least a firstand second support structures formed opposite each other and extendinggenerally perpendicularly from the flange wherein the support structuresare configured to stably support the package on a flat surface.103. The hydrogel contact lens system of embodiment 102 furthercomprising as a component of the packaging system a packaging solutioncomprising at least one component selected from the group consisting ofanionic polymers such as Poly(acrylic acid), Poly(acrylamide-co-acrylicacid) or Carboxymethylcellulose; Cationic Polymers such as Polymer JR orpolymers having latent amines; Zwitterionic components such asphosphocholine, polyphosphocholine or latent amino acids; Polypeptidessuch as Poly(glutamic acid) or Poly(lysine); Non-Ionic Surfactants suchas Tetronic T1107, Tetronic T908, Hydroxypropyl methylcellulose,Silicone surfactants (NVP-co-TRIS VC) or Glycereth cocoate and mixturesany of the above packaging solution components.104. The hydrogel contact lens system of embodiments 102 or 103 whereineach support structure includes a major wall and a minor wall lying ingenerally spaced, parallel planes to each other.105. The hydrogel contact lens system of embodiment 104 wherein themajor and minor walls interconnect or touch along one or more pointsthereof.106. The hydrogel contact lens system of any one of embodiments 102-105wherein the minor wall is located inwardly of a respective major wall.107. A mono ethylenically unsaturated polymerizable group containingpolycarbosiloxane monomer as substantially shown and described herein.108. A monomer mix comprising a mono ethylenically unsaturatedpolymerizable group containing polycarbosiloxane monomer and at leastone other monomer as substantially shown and described herein.109. A medical device comprising a polymerized monomer mix comprising amono ethylenically unsaturated polymerizable group containingpolycarbosiloxane monomer and at least one other monomer assubstantially shown and described herein.110. The medical device of embodiment 109 wherein the medical device iscoated with a coating material comprising at least one of the followingmaterials HEMA, glyceryl methacrylate, methacrylic acid (“MAA”), acrylicacid (“AA”), methacrylamide, acrylamide, N,N′-dimethylmethacrylamide, orN,N′-dimethylacrylamide; copolymers thereof; hydrophilic prepolymers,such as ethylenically unsaturated poly(alkylene oxide)s, cyclic lactamssuch as N-vinyl-2-pyrrolidone (“NVP”), or derivatives thereof,hydrophilic vinyl carbonate or vinyl carbamate monomers as substantiallyshown and described herein.111. A hydrogel contact lens system comprising a polymerized monomermixture of any one of the monomer mixes of embodiments 18-94 placed in apackage which comprises a flange with a well formed therein for holdinga contact lens in solution, a flexible cover sheet which extends overthe flange and is sealed about the perimeter of the well to seal thelens and solution in the well wherein the package has at least a firstand second support structures formed opposite each other and extendinggenerally perpendicularly from the flange wherein the support structuresare configured to stably support the package on a flat surface whereinthe solution is a packaging solution comprising at least one componentselected from the group consisting of anionic polymers such asPoly(acrylic acid), Poly(acrylamide-co-acrylic acid) orCarboxymethylcellulose; Cationic Polymers such as Polymer JR or polymershaving latent amines; Zwitterionic components such as phosphocholine,polyphosphocholine or latent amino acids; Polypeptides such asPoly(glutamic acid) or Poly(lysine); Non-Ionic Surfactants such asTetronic T1107, Tetronic T908, Hydroxypropyl methylcellulose, Siliconesurfactants (NVP-co-TRIS VC) or Glycereth cocoate and mixtures any ofthe above packaging solution components as substantially shown anddescribed herein.112. A method of making a hydrogel contact lens comprising as acomonomer in a polymerized monomer mixture a mono ethylenicallyunsaturated polymerizable group containing polycarbosiloxane monomerwherein the method is performed as substantially shown and describedherein.113. A hydrogel contact lens system comprising as part of a packagingsolution in the hydrogel contact lens system polyphosphorylcholine.

It will be understood that various modifications may be made to theembodiments disclosed herein. Therefore the above description should notbe construed as limiting, but merely as exemplifications of preferredembodiments. For example, the functions described above and implementedas the best mode for operating the present invention are forillustration purposes only. Other arrangements and methods may beimplemented by those skilled in the art without departing from the scopeand spirit of this invention. Moreover, those skilled in the art willenvision other modifications within the scope and spirit of the featuresand advantages appended hereto.

1. A hydrogel contact lens comprising a polymerized monomer mixcomprising a polymerizable monomer mixture comprising about 0.1 to about75.8 percent by weight of a methacrylamide crosslinker, about 0 to about41.2 percent by weight of a bulky siloxane monomer, about 0 to about 78percent by weight of at least one hydrophilic monomer, about 0 to about48.6 percent by weight of an alcohol, about 0.1 to about 29.9 weightpercent of an mono ethylenically unsaturated polymerizable groupcontaining polycarbosiloxane monomer, about 0.1 to about 1.0 percent byweight of an initiator and about 90 to about 200 parts per million of avisibility tint.
 2. The hydrogel contact lens of claim 1 comprising aspart of polymerizable monomer mixture comprising about 5 to about 13percent by weight of a methacrylamide crosslinker, about 34 to about 41percent by weight of a bulky siloxane monomer, about 28 to about 52percent by weight of at least one hydrophilic monomer, about 0 to about25 percent by weight of an alcohol, about 5 to about 15 weight percentof an mono ethylenically unsaturated polymerizable group containingpolycarbosiloxane monomer, about 0.2 to about 0.8 percent by weight ofan initiator and about 90 to about 145 parts per million of a visibilitytint.
 3. The hydrogel contact lens of claim 1 comprising as part ofpolymerizable monomer mixture comprising about 2 to about 8 percent byweight of a methacrylamide crosslinker, about 25 to about 38 percent byweight of a bulky siloxane monomer, about 35 to about 45 percent byweight of at least one hydrophilic monomer, about 3 to about 8 percentby weight of an alcohol, about 10 to about 13 weight percent of an monoethylenically unsaturated polymerizable group containingpolycarbosiloxane monomer, about 0.3 to about 0.6 percent by weight ofan initiator and about 145 to about 200 parts per million of avisibility tint.
 4. The hydrogel contact lens of any one of claims 1-3wherein the mono ethylenically unsaturated polymerizable groupcontaining polycarbosiloxane monomer is a monomer having a structuralformula (I):

wherein X is the residue of a ring opening agent or a capping agent; Lis the same or different and is a linker group or a bond; V is anethylenically unsaturated polymerizable group; R₁, R₂, R₃, R₄, R₅, R₆are independently H, alkyl, halo alkyl, heteroalkyl, cyclo alkyl,heterocyclo alkyl, alkenyl, halo alkenyl, or aromatic; R₇ and R₈ whenpresent are independently H or alkyl wherein at least one of R₇ or R₈ ishydrogen; y is 2-7 and n is 1-100.
 5. The hydrogel contact lens of anyone of claims 1-3 wherein the mono ethylenically unsaturatedpolymerizable group containing polycarbosiloxane monomer is a monomerhaving a structural formula (II)

wherein L is the same or different and is a linker group or a bond and Vis the same or different and is an ethylenically unsaturatedpolymerizable group, R₁, R₂, R₃, R₄, R₅, R₆ and R₉ are independently H,alkyl, halo alkyl, cyclo alkyl, heterocyclo alkyl, alkenyl, haloalkenyl, or aromatic, R₇ and R₈ are independently H or alkyl wherein atleast one of R₇ or R₈ is hydrogen, y is 2-7 and n is 1-100.
 6. Thehydrogel contact lens of claim 4 wherein X is a residue of a ringopening agent selected from the group consisting of alkyl lithiums,alkoxides, trialkylsiloxylithiums and acrylic ester-capped polysiloxaneprepolymers in the presence of an acid catalyst.
 7. The hydrogel contactlens of claim 4 or 5 wherein the linker group is selected from the groupconsisting of substituted or unsubstituted alkyl, alkyl ether, alkenyls,alkenyl ethers, halo alkyls, substituted or unsubstituted siloxanes, andmonomers capable of propagating ring opening.
 8. The hydrogel contactlens of any one of claims 1-3 wherein the mono ethylenically unsaturatedpolymerizable group containing polycarbosiloxane monomer is a monomerhaving a structural formula (III):

wherein R₉, R₁₀ and R₁₁ are independently H, alkyl, haloalkyl or othersubstituted alkyl groups, n is 1-100 and n¹ is 0-10.
 9. The hydrogelcontact lens of any one of claims 1-3 wherein the mono ethylenicallyunsaturated polymerizable group containing polycarbosiloxane monomer isa monomer having a structural formula (IV):

wherein n is 1-100.
 10. The hydrogel contact lens of claim 9 wherein nis 2-80.
 11. The hydrogel contact lens of claim 9 wherein n is 3-20. 12.The hydrogel contact lens of claim 9 wherein n is 5-15.
 13. The hydrogelcontact lens of claim 4 or 5 wherein V is selected from the groupconsisting of acrylates, methacrylates, vinyl carbonates, O-vinylcarbamates, N-vinyl carbamates, acrylamides and methacrylamides.
 14. Thehydrogel contact lens of claim 4 wherein the mono ethylenicallyunsaturated polymerizable group containing polycarbosiloxane monomer isa monomer having a structural formula selected from the group consistingof the following structural formulae:


15. The hydrogel contact lens of claim 4 wherein the mono ethylenicallyunsaturated polymerizable group containing polycarbosiloxane monomer isa monomer having a structural formula selected from the group consistingof the following structural formulae:

wherein R₉, R₁₀ and R₁₁ are independently H, alkyl, haloalkyl or othersubstituted alkyl groups and n is 1-100 and n¹ is 0-10.
 16. The hydrogelcontact lens of claim 4 wherein the mono ethylenically unsaturatedpolymerizable group containing polycarbosiloxane monomer is a monomerhaving a structural formula selected from the group consisting of thefollowing structural formulae:

wherein n is 1-100 and X⁻ is a counterion to provide an overall neutralcharge.
 17. The hydrogel contact lens of claim 4 wherein the monoethylenically unsaturated polymerizable group containingpolycarbosiloxane monomer is a monomer having the following structuralformula: